Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids

ABSTRACT

Disclosed is an improved method of making polymers. The method utilizes at least one ethylenically unsaturated monomer and at least one polymerizable surface active agent. The polymerizable surface active agent is capable of co-polymerization with traditional monomers and/or polymerization with itself (i.e. homopolymerization) and is preferably substantially completely consumed during the course of the polymerization. Polymers produced by the method of the present invention are well suited for use in coatings, adhesives, sealants, elastomers and the like, as they form stable films, possess excellent adhesion properties and have improved hydrolytic stability characteristics. The present invention also encompasses homopolymeric surface active agents and their use in polymerization reactions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an improved emulsion polymerizationprocess utilizing ethylenically unsaturated amine salts of sulfonic,phosphoric and carboxylic acids. More specifically, the inventionrelates to emulsion polymerization processes which utilize ethylenicallyunsaturated amine salts of alkylbenzene sulfonic acids, alkyl olefinsulfonic acids, alkyl alcohol sulfuric acid esters, or alkoxylated alkylalcohol sulfuric acid esters, fatty acids, and fatty phosphate acidesters, or mixtures thereof, to form polymers, discrete solid polymericparticles and latexes. Additionally, the present invention relates tothe use of the salts to impart improved adhesion, hydrophobicity,resistance to film yellowing, scrubability, anti-blooming, hydrolyticstability and shear stability characteristics to polymer emulsions andlatex formulations.

2. Description of the Related Art

The emulsion polymerization of ethylenically unsaturated monomers toform discrete solid polymeric particles for use in coating, sealant,adhesive and/or elastomer (CASE) applications is well known to the art.Conventional emulsion polymerization of ethylenically unsaturatedmonomers employs one or more water soluble surfactants to emulsify themonomers and the resulting polymer products, i.e., latexes. The monomersused in emulsion polymerization reactions are generally water-insoluble,but in some cases may be water-soluble. During a typical emulsionpolymerization, a surfactant is used to suspend small portions ofmonomer in a continuous or semi-continuous aqueous phase. Typically, themonomer molecules are suspended as small spheres in the aqueous phase,wherein the polymerization takes place within the small spheres. Thewater soluble surface active agents, i.e., surfactants, typicallyutilized in emulsion polymerization reactions are anionic, nonionic, andcationic surfactants or a mixture thereof.

The polymeric particles formed by the emulsion polymerization processare typically utilized in coating, sealant, adhesive and/or elastomer(CASE) applications. In a traditional emulsion polymerization reaction,the surfactant does not become chemically bonded to the polymericparticles by carbon-carbon bond formation but rather remains in thepolymeric particle product solution after the emulsion polymerizationreaction is complete, i.e., all of the monomer(s) is reacted. Theunreacted surfactant can have a detrimental effect on the polymerproduct solution, as it can interfere with the performance of suchpolymerization products in CASE applications; the suspension ofpolymeric particles may become destabilized over time and undergounwanted coagulation. The unreacted surfactant may cause unwantedpealing of a latex paint coating on a substrate, and decreased moistureand scrubability resistance in other various CASE applications.Additionally, residual surfactant can cause an undesirable “blooming”that leads to surface irregularities in a resulting CASE material thatis applied to a substrate.

Several proposals have been made in the prior art to employ apolymerizable surfactant as the surface active agent during an emulsionpolymerization reaction. U.S. Pat. No. 5,478,883 (incorporated herein byreference in its entirety) describes the use of ethylenicallyunsaturated polymerizable water-soluble nonionic surfactants formed bythe reaction of a diallylamine compound with ethylene oxide, propyleneoxide or butylene oxide, in emulsion polymerization reactions.Similarly, U.S. Pat. No. 5,162,475 (incorporated herein by reference)provides alpha-beta ethylenically unsaturated poly(alkylenoxy)polymerizable surface active compounds for use in emulsionpolymerization. For additional examples of polymerizable surfactants foruse in emulsion polymerization processes, see U.S. Pat. Nos. 4,377,185and 4,049,608.

Non-polymerizable surfactant solutions to the traditional problemsencountered in performing an emulsion polymerization process arenumerous. U.S. Pat. No. 3,941,857 describes the use of epoxy resinswhich react with the residual anionic, cationic or nonionic surfactant.Polymerizable compounds such as allyl alcohol (and esters thereof) havebeen found to be ineffective due to the formation of undesirable highlevels of coagulum in the final emulsion polymerization product.Additionally, see U.S. Pat. No. 4,224,455.

Thus, there is a need for an emulsion polymerization process for formingpolymers and discrete polymeric particles that are well suited for usein coatings (e.g., latex paints, electro-deposition, container, paperand paperboard, can coatings, industrial coatings, automotive coatings,textile coatings), adhesive (e.g., water- and non-water borne adhesives,pressure sensitive adhesives, binders), sealant (e.g. floor finishes,films, binders, non-woven binding materials such as carpet backing,glass fibers) and elastomer (CASE) applications.

SUMMARY OF THE INVENTION

The present invention utilizes a novel group of compounds in the form ofethylenically unsaturated amine salts of sulfonic, phosphoric andcarboxylic acids, which display surface activity, i.e. they aresurfactants. It has been discovered that these compounds function asreactive surfactants, i.e. surface active agents in polymerizationprocesses, particularly emulsion polymerization processes. The surfaceactive agents of the present invention are capable of polymerizing withthemselves (to form homopolymeric surface active agents) and/or arecapable of co-polymerizing with other ethylenically unsaturated monomersof the type which are commonly employed in polymerization processes. Thepolymerizable surface active agents utilized in the present inventionare prepared from readily available, economical raw materials, andgenerally, their preparation does not require any special handling orequipment.

Accordingly, an improved method is provided for forming polymersutilizing polymerizable surface active agents detailed herein.Generally, the improved method comprises:

a) preparing a mixture comprising:

i) at least one ethylenically unsaturated monomer;

ii) at least one polymerizable, surface active agent;

wherein the polymerizable, surface active agent is a salt or quaternarynitrogen compound comprising:

a) at least one acid, wherein the acid is a sulfonic acid, a carboxylicacid, or a phosphoric acid, or a mixture thereof; and

b) at least one nitrogenous base, wherein the nitrogenous base containsat least one nitrogen atom and at least one ethylenically unsaturatedmoiety; and

b) polymerizing the mixture;

wherein the polymerizable, surface active agent is capable ofpolymerization with itself, copolymerization with the ethylenicallyunsaturated monomer or co-polymerization with a partially polymerizedpolymer particle. Somewhat preferably, the nitrogen atom is linkedcovalently, directly or indirectly, to the ethylenically unsaturatedmoiety of the nitrogenous base.

The polymers prepared utilizing the polymerizable surface active agentsof the present invention may be used as the primary resin component or aminor resin component of a resin mixture which is used to preparelatexes, coatings, adhesives, sealants, elastomers, binders, inks, floorfinishes and the like. A polymer is defined herein as a product producedby polymerizing two or more monomers, which may be the same ordifferent. Additionally, the polymer may have incorporated into it,surface active agent monomers and/or homopolymeric surface activeagents. The various final compositions, application and polymer productsdescribed herein may contain various optional ingredients such asfillers, pigments, colorants, solvents, plasticizers, antioxidants,curing agents, thickeners, non-polymerizable surface active agents(surfactants), preservatives, wet strength additives, and the like.

The present invention provides an improved polymerization process forforming polymers, wherein the polymerizable surface active agent used inthe polymerization reaction does not interfere with the quality of theCASE applications. Various classes of polymers formed in the presentinvention, upon application to textiles, fabrics, and other substrates,may reduce the shrinkage of cotton fabrics, cotton/polyester blendfabrics, cotton/rayon blend fabrics, rayon fabrics, and cellulosic orcellulosic/synthetic blend fabrics.

The present invention provides an improved polymerization process, formaking suspension or dispersions of polymers which exhibit enhancedmechanical stability and the ability to withstand freezing and thawingwhile at the same time retaining good dispersion or suspension.

The present invention provides an improved polymerization process,wherein the resulting polymers exhibit/impart improved adhesion of aCASE to a substrate, e.g. they are substantially resistant to pealingand cracking.

The present invention provides an improved polymerization process,wherein the resulting polymers exhibit/impart improved anti-yellowingproperties when employed in a CASE application.

The present invention provides an improved polymerization process,wherein the resulting polymers exhibit/impart improved scrubabilityproperties of a CASE application.

The present invention provides an improved polymerization process,wherein the resulting polymers exhibit/impart improved solventresistance properties when employed in a CASE application.

The present invention provides an improved polymerization process,wherein the resulting polymers exhibit/impart improved film rewetproperties when employed in a CASE application.

The present invention provides an improved polymerization process,wherein coatings formed, using the polymers of the present invention,remain uniform and stable upon the passage of time and/or exposure tomoisture at ambient or elevated temperature.

The present invention provides polymers suitable for use in coating,adhesive, sealant and/or elastomer (CASE) applications. The polymers maybe in a variety of forms, such as, for example, solids, flakes, powders,semi-solids, thick pastes, flowable/pumpable pastes (i.e. G-phasepastes), liquids, gels, “ringing” gels, dilute or concentrated solutionsand the like. The polymers may be spray dried, flaked, extruded, or thelike.

The present invention additionally provides homopolymeric surface activeagents comprised of polymerized, polymerizable surface active agents orblends of polymerizable surface active agents. These homopolymericsurface active agents are useful in the polymerization processesdetailed herein. The present invention further provides homopolymericsurface active agent/polymerizable surface active agent blends comprisedof partially polymerized, polymerizable surface active agents andnon-polymerized, polymerizable surface active agents. Thesehomopolymeric/polymerizable surface active agent blends are also usefulin the polymerization processes detailed herein.

The improved polymerization process of the present invention preferablydoes not require the use of a surfactant which contains residualformaldehyde or other low molecular weight volatile organic compounds.However, while not usually desirable, low molecular weight volatileorganic compounds and/or residual formaldehyde may be present in thepolymerization products of the present invention. Further, thepolymerization process of the present invention provides latexes withimproved shear stability, improved pH stability, improved shelf storagestability and improved ease of viscosity modification.

The polymerizable surface active agent may be added to the mixture in abatch mode (i.e. all at once), a continuous mode (i.e. by addition of anamount of the polymerizable surface active agent throughout thepolymerization) or in a semi-continuous mode (i.e. addition of portionsof the polymerizable surface active agent at various times during thepolymerization).

The polymerizable surface active agents utilized in the presentinvention are generally formed by combining at least one acid, whereinthe acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, ora mixture thereof, with a nitrogenous base, wherein the nitrogenous basecontains at least one nitrogen atom and at least one ethylenicallyunsaturated moiety. The polymerizable surface active agents of thepresent invention generally contain a quaternary nitrogen atom and arein the form of salts or quaternary nitrogen compounds.

Various functional groups may be incorporated in the polymerizablesurfactants of the present invention, in either the acid or thenitrogenous base, to form specialty polymerizable surface active agents.These specialty polymerizable surface active agents may posses variousproperties such as, for example, biocidal activity, herbicidal activity,pesticidal activity, anti-static activity and the like, either before orafter polymerization with known monomers or polymerization withthemselves. Additionally, the polymerizable surface active agents of thepresent invention may be utilized in forming biodegradable polymers,photoreactive polymers, sunscreen enhancing polymers, fabric softeningpolymers, polyol polymers, ophthalmic polymers, lubricants and the like.

These and other objects and advantages, as well as the scope, nature,and utilization of the claimed invention will become apparent to thoseskilled in the art from the following detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. I is a partial ¹H NMR spectrum, showing the region of δ 5.0-8.0, ofthe allylamine salt of dodecylbenzenesulfonic acid (ADDBS).

FIG. II is a partial ¹H NMR spectrum, showing the region of δ 5.0-8.0,of a latex formulation prepared according to Example #1.

DETAILED DESCRIPTION OF THE INVENTION

A method is provided for forming polymers utilizing polymerizablesurface active agents, wherein the method comprises: (1) preparing amixture comprising at least one ethylenically unsaturated monomer and atleast one polymerizable surface active agent; and (2) polymerizing themixture. Generally, any ethylenically unsaturated monomer that iscapable of undergoing polymerization may be utilized in the presentinvention. The method of the present invention is particularly wellsuited to emulsion polymerization but may also be conducted as asolution polymerization, suspension polymerization, micro emulsionpolymerization or inverse emulsion polymerization. The polymerizationmay be conducted in any manner known to the art, including but notlimited to, free-radical initiated polymerization, thermal initiatedpolymerization and redox initiated polymerization using, for example,batch, continuous, or controlled monomer feed processes, knownconditions of stirring time and temperature, and known kinds ofadditives such as initiators, surfactants, electrolytes, pH adjustingagents, buffering agents, protective colloids and the like. In general,the polymerization process of the present invention will be carried outfrom about 20° C. to about 120° C. (e.g., between about 50° C. and about110° C.). These polymerization temperatures will vary with respect tothe reactivity and concentration of the polymerization initiator beingused. Batch polymerization times may vary depending on the method ofpolymerization and the monomers being polymerized. Such times may varyfrom about 2 to about 10 hours. In general, the mixture may be asolution, emulsion, suspension or dispersion of the ethylenicallyunsaturated monomer and the polymerizable surface active agent. Further,the polymerizable surface active agent may be provided to the mixture asan aqueous solution.

In accordance with the present invention, polymerization may occursimultaneously as the mixture is being formed (i.e. as the monomer andthe polymerizable surface active agent come in contact, aself-initiating polymerization occurs). Accordingly, the presentinvention also encompasses a method for continuous polymerization,utilizing at least one ethylenically unsaturated monomer and at leastone polymerizable surface active agent.

The polymerizable, surface active agents utilized in the presentinvention are salts or quaternary nitrogen compounds comprising:

a) at least one acid, wherein the acid is a sulfonic acid, a carboxylicacid, or a phosphoric acid, or a mixture thereof; and

b) at least one nitrogenous base, wherein the nitrogenous base containsat least one nitrogen atom and at least one ethylenically unsaturatedmoiety.

The polymerizable surface active agents are generally capable ofpolymerization with themselves, copolymerization with the ethylenicallyunsaturated monomer or co-polymerization with a partially polymerizedpolymer particle. In a somewhat preferred embodiment, the polymerizablesurface active agent is partially (i.e. 1-50 percent by weight of thepolymerizable surface active agent) consumed by polymerization withitself, co-polymerization with the monomer and/or co-polymerization witha partially polymerized polymer particle. In a more preferredembodiment, the polymerizable, surface active agent is substantially(i.e. 50-90 percent by weight of the polymerizable surface active agent)consumed by polymerization with itself, co-polymerization with themonomer and/or co-polymerization with a partially polymerized polymerparticle. In a most preferred embodiment, the polymerizable, surfaceactive agent is substantially completely (i.e. greater than 90 percentby weight of the polymerizable surface active agent) consumed bypolymerization with itself, co-polymerization with the monomer and/orco-polymerization with a partially polymerized polymer particle.

The polymerizable surface active agent and the monomer are generallycombined in a ratio of about 0.01:1 to about 3:1 on a weight basis. In apreferred embodiment, the polymerizable surface active agent is presentin the mixture in a concentration of about 1-100 weight percent, basedon the total weight of the ethylenically unsaturated monomer present inthe mixture. In a more preferred embodiment, the polymerizable surfaceactive agent is present in the mixture in a concentration of about 1-20weight percent, based on the total weight of the ethylenicallyunsaturated monomer present in the mixture.

In general, the method of preparing polymers in accordance with thepresent invention does not require the use of a non-polymerizablesurfactant, i.e. the mixture is substantially free of non-polymerizable,surface active agents. However, in a somewhat less preferred embodiment,the mixture further comprises a supplemental, non-polymerizablesurfactant (iii); wherein the supplemental surfactant is a sodium,potassium, calcium, magnesium, or ammonium salt of a substantiallysaturated anionic surfactant, or a nonionic, cationic, or amphotericsurfactant, or a mixture thereof; and wherein the supplementalsurfactant is provided in a concentration of about 0.01 to about 20.0percent by weight, based on the total weight of polymerizable surfaceactive agent and supplemental surfactant provided in the reaction zone.

The present invention provides pre-polymerization mixtures comprising(1) at least one ethylenically unsaturated monomer; and (2) at least onepolymerizable surface active agent;

wherein the ethylenically unsaturated monomer and the polymerizablesurface active agent are defined as above or below. Thispre-polymerization mixture may be polymerized by a variety of initiationmethods known to the art.

The present invention provides polymers comprising: (1) at least onemonomer unit; and (2) at least one surface active agent unit; whereinthe monomer unit is derived from an ethylenically unsaturated monomer;wherein the surface active agent is derived from a polymerizable surfaceactive agent; and wherein the ethylenically unsaturated monomer and thepolymerizable surface active agent have co-polymerized to form thepolymer.

In another embodiment, the present invention provides a method forforming polymers, wherein the method comprises (1) preparing a mixturecomprising at least one ethylenically unsaturated monomer, at least oneacid, wherein the acid is a sulfonic acid, a carboxylic acid, or aphosphoric acid, or a mixture thereof, and at least one nitrogenousbase, wherein the nitrogenous base contains at least one nitrogen atomand at least one ethylenically unsaturated moiety; and (2) polymerizingthe mixture. In accordance with this embodiment, the acid and thenitrogenous base may form a polymerizable, surface active agent in situ;wherein the polymerizable, surface active agent is a salt or quaternarynitrogen compound; wherein the polymerizable surface active agent iscapable of polymerization with itself, copolymerization with theethylenically unsaturated monomer and/or co-polymerizing with apartially polymerized polymer particle; and wherein the polymerizable,surface active agent is substantially completely consumed bypolymerization with itself, co-polymerization with the monomer and/orco-polymerization with a partially polymerized polymer particle. In onealternative, the nitrogenous base may partially or completelyco-polymerize with the ethylenically unsaturated monomer, followed byformation of a surface active agent (i.e. complexation/salt formationwith the acid). Without being bound by any particular theory, it isbelieved that the nitrogenous base is incorporated into the polymerback-bone and the acid forms an ion pair, i.e. a salt, with the nitrogenatom of the nitrogenous base, thereby adhering to the polymer andforming a positively charged nitrogen atom. In another alternativewithin the purview of this embodiment, a portion of the nitrogenous basemay polymerize with itself, co-polymerizes with the ethylenicallyunsaturated monomer or co-polymerize with a partially polymerizedpolymer, followed by complexation/salt formation with the acid. Inanother alternative, the nitrogenous base may partially or completelyco-polymerize with a homopolymeric surfactant, followed bycomplexation/salt formation with the acid.

The present invention provides polymers comprising: (1) at least onemonomer unit; (2) at least one acid, wherein the acid is a sulfonicacid, a carboxylic acid, or a phosphoric acid, or a mixture thereof, andat least one nitrogenous base, wherein the nitrogenous base contains atleast one nitrogen atom and at least one ethylenically unsaturatedmoiety; wherein the monomer unit is derived from an ethylenicallyunsaturated monomer; wherein the nitrogenous base is homopolymerized,co-polymerized with the monomer, and/or polymerized with a partiallypolymerized polymer, wherein the acid complexes to the nitrogen atom(s),to form a salt- or a quaternary nitrogen-containing polymer.

In another embodiment, the present invention provides a method forforming polymers, wherein the method comprises: (1) preparing a mixturecomprising at least one ethylenically unsaturated monomer and at leastone homopolymeric surface active agent, the homopolymeric surface activeagent being a polymer formed by polymerizing at least one polymerizable,surface active agent; wherein the polymerizable, surface active agent isa salt or quaternary nitrogen compound comprising at least one acid,wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoricacid, or a mixture thereof, and at least one nitrogenous base, whereinthe nitrogenous base contains at least one nitrogen atom and at leastone ethylenically unsaturated moiety; and (2) polymerizing the mixture.

The present invention provides homopolymeric surface active agents.These homopolymeric surface active agents are formed by polymerizing atleast one polymerizable, surface active agent, wherein thepolymerizable, surface active agent is a salt or quaternary nitrogencompound comprising at least one acid, wherein the acid is a sulfonicacid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; andat least one nitrogenous base, wherein the nitrogenous base contains atleast one nitrogen atom and at least one ethylenically unsaturatedmoiety. Optionally, the homopolymeric surface active agents may beformed by partially or completely polymerizing the nitrogenous base,followed by complexation of the resulting polymer with the acid, whereinthe acid complexes to the nitrogen atom(s), to form a salt- or aquaternary nitrogen-containing homopolymeric surface active agent.

The homopolymeric surface active agents of the invention are generallycapable of polymerization with themselves, co-polymerization with themonomer or co-polymerization with a partially polymerized polymer.

In another embodiment, the present invention provides a method forforming polymers, wherein the method comprises: (1) partiallypolymerizing at least one ethylenically unsaturated monomer to form apartially polymerized polymer/monomer mixture; (2) adding to thepartially polymerized polymer/monomer mixture at least one polymerizablesurface active agent and/or at least one homopolymeric surface activeagent, to form a partially polymerized polymer/monomer/surface activeagent mixture; and (3) polymerizing the partially polymerized polymer/monomer/surface active agent mixture; wherein the homopolymeric surfaceactive agent being a polymer formed by polymerizing at least onepolymerizable, surface active agent; wherein the polymerizable, surfaceactive agent is a salt or quaternary nitrogen compound comprising atleast one acid, wherein the acid is a sulfonic acid, a carboxylic acid,or a phosphoric acid, or a mixture thereof, and at least one nitrogenousbase, wherein the nitrogenous base contains at least one nitrogen atomand at least one ethylenically unsaturated moiety.

In another embodiment, the present invention provides a method forforming polymers, wherein the method comprises: (1) preparing a mixturecomprising at least one ethylenically unsaturated monomer and at leastone non-polymerizable, supplemental surface active agent; (2) partiallypolymerizing the mixture to form a partially polymerizedpolymer/monomer/supplemental surface active agent mixture; (3) adding tothe partially polymerized polymer/monomer/supplemental surface activemixture at least one polymerizable surface active agent and/or at leastone homopolymeric surface active agent, to form a partially polymerizedpolymer/monomer/supplemental surface active agent/polymerizable surfaceactive agent mixture; and (4) polymerizing the partially polymerizedpolymer/monomer/surface active agent/polymerizable surface active agentmixture; wherein the homopolymeric surface active agent being a polymerformed by polymerizing at least one polymerizable, surface active agent;wherein the polymerizable, surface active agent is a salt or quaternarynitrogen compound comprising at least one acid, wherein the acid is asulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixturethereof, and at least one nitrogenous base, wherein the nitrogenous basecontains at least one nitrogen atom and at least one ethylenicallyunsaturated moiety; and wherein the supplemental surface active agent isgenerally non-polymerizable and is defined herein.

In another embodiment, the present invention provides a method forforming polymers, and suspension or dispersions of polymers, wherein themethod comprises: (1) preparing a mixture comprising at least oneethylenically unsaturated monomer and at least one non-polymerizable,supplemental surface active agent; (2) polymerizing the mixture to forma polymer mixture; and (3) adding at least one polymerizable surfaceactive agent and/or at least one homopolymeric surface active agent tothe polymer mixture; wherein the homopolymeric surface active agentbeing a polymer formed by polymerizing at least one polymerizable,surface active agent; wherein the polymerizable, surface active agent isa salt or quaternary nitrogen compound comprising at least one acid,wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoricacid, or a mixture thereof, and at least one nitrogenous base, whereinthe nitrogenous base contains at least one nitrogen atom and at leastone ethylenically unsaturated moiety.

The present invention encompasses polymers prepared by any of themethods or processes described herein. Generally, the methods of thepresent invention encompass, emulsions, suspensions or dispersion ofpolymer obtained therefrom.

ETHYLENICALLY UNSATURATED MONOMERS

The ethylenically unsaturated monomer or monomers that may bepolymerized or copolymerized according to the present invention areknown to the art and are described below in a representative manner.Examples of suitable ethylenically unsaturated monomers are, forexample, mono- and polyunsaturated hydrocarbon monomers, vinyl esters(e.g., vinyl esters of C₁ to C₆ saturated monocarboxylic acids), vinylethers, monoethylenically unsaturated mono- and polycarboxylic acids andthere alkyl esters (e.g., acrylic acid esters and methacrylic acidesters, particularly the C₁ to C₁₂ alkyl, and more particularly the C₁to C₄ alkyl esters), the nitrites, vinyl and vinylidene halides, andamides of unsaturated carboxylic acids and amino monomers.

Examples of suitable hydrocarbon monomers for use in the presentinvention include styrene compounds (e.g., styrene, carboxylatedstyrene, and alpha-methyl styrene), ethylene, propylene, butylene, andconjugated dienes (e.g., butadiene, isoprene and copolymers of butadieneand isoprene). Examples of vinyl and vinylidene halides include vinylchloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.

Examples of acrylic esters and methacrylic esters suitable for use inthe present invention include C₁-C₁₂ (e.g., C₁-C₄) alkyl acrylates andmethacrylates. Typical alkyl esters and methacrylic esters includemethyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, isopropyl methacrylate, n-butylacrylate, n-butyl methacrylate, isobutyl acrylate, isobutylmethacrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-dimethylbutylacrylate, 3,3-dimethyl butyl methacrylate, and lauryl acrylate.

Suitable vinyl esters for use in the present invention include aliphaticvinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate,vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate,and allyl esters of saturated monocarboxylic acids, such as allylacetate, allyl propionate and ally lactate.

Vinyl ethers suitable for use in the present invention includemethylvinyl ether, ethylvinyl ether and n-butylvinyl ether. Typicallyvinyl ketones include methylvinyl ketone, ethylvinyl ketone andisobutylvinyl ketone. Suitable dialkyl esters of monoethylenicallyunsaturated dicarboxylic acids include dimethyl maleate, diethylmaleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonylmaleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate,diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate,diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethylitaconate, dibutyl itaconate, and dioctyl itaconate.

Monoethylenically unsaturated monocarboxylic acids suitable for use inthe present invention include acrylic acid, methacrylic acid, ethacrylicacid, and crotonic acid. Suitable monoethylenically unsaturateddicarboxylic acids include maleic acid, fumaric acid, itaconic acid andcitraconic acid. Suitable monoethylenically unsaturated tricarboxylicacids include aconitic acid and the halogen-substituted derivatives(e.g., alphachloracylic acid), and the anhydrides of these acids (e.g.,maleic anhydride and citraconic anhydride).

Nitriles of the above ethylenically unsaturated mono-, di- andtricarboxylic acids which are suitable monomers include acrylonitrile,alpha-chloroacrylonitrile and methacrylonitrile. Suitable amides ofthese carboxylic acids include unsubtituted amides such as acrylamide,methacrylamide and other alpha-substituted acrylamides and N-substitutedamides obtained by the reaction of the amides of the aforementionedmono- and polycarboxylic acids with and aldehyde (e.g., formaldehyde).Typical N-substituted amides include N-methylolacrylamide,N-methylolmethacrylamide alkylated N-methylolacrylamides andN-methylolmethacrylamides (e.g., N-methyoxymethylacrylamide andN-methoxymethylmethacrylamide).

Amino monomers useful in the present invention include substituted andunsubstituted aminoalkyl acrylates, hydrochloride salts of aminomonomers and methacrylates, such as beta-aminoethylacrylate,beta-amino-ethylmethacrylate, dimethylaminomethylacrylate,beta-methylaminoethylacrylate, and dimethylaminomethylmethacrylate.

Hydroxy-containing monomers useful in the present invention includebeta-hydroxyethylacrylate, beta-hydroxypropylacrylate,gamma-hydroxypropylacrylate and beta-hydroxyethylmethacrylate.

Monomers useful in the present invention may be homopolymerized orcopolymerized, i.e., one or more different monomers capable ofpolymerization may be used.

POLYMERIZABLE SURFACE ACTIVE AGENTS

The polymerizable surface active agents utilized in the presentinvention are salts or quaternary nitrogen compounds comprising at leastone acid, wherein the acid is a sulfonic acid, a carboxylic acid, or aphosphoric acid, or a mixture thereof, and at least one nitrogenousbase, wherein the nitrogenous base contains at least one nitrogen atomand at least on ethylenically unsaturated moiety. The polymerizablesurface active agents is usually present in the mixture in aconcentration from about 0.01-100.0 percent by weight based on the totalweight of the ethylenically unsaturated monomer. In general, althoughnot required, the polymerizable surface active agents have ahomophilic/lipophilic balance (HLB) of less than about 45. In a somewhatmore preferred embodiment, the polymerizable surface active agents havean HLB of about 5-40. The polymerizable surface active agents aregenerally capable of polymerization with themselves, co-polymerizationwith the ethylenically unsaturated monomer, or co-polymerization with apartially polymerized polymer.

More specifically, while the nitrogenous base may be capable of somedegree of surface activity, in the present invention it is the acidportion of the polymerizable surfactant that is responsible for thesurfactant character and the HLB of the compound. In preferredembodiments, the nitrogenous base contributes little or no surfactantcharacter to these materials. In other words, the acids are generallycapable of acting as surfactants when they are present as anions of theacid and the associated counterion is any positively charged species.The most common positively charged species are sodium, potassium,ammonium, calcium and magnesium ions. In fact, the acid portion of thepolymerizable surfactant may be supplied as a sodium, potassium, orother salt of the carboxylic, phosphoric or sulfonic acid and thencombined with the nitrogenous base to form the inventive surfactant.

The polymerizable surface active agents of the present invention areprepared from readily available, economical raw materials, andgenerally, their preparation does not require any special handling orequipment. The polymerizable surface active agents may be prepared in abatch mode or a continuous mode; they may be prepared by contactingnitrogenous base with the acid or contacting the acid with thenitrogenous base. By contacting it is meant that the acid(s) is added tothe nitrogenous base and the components are mixed, or the ethylenicallyunsaturated amine(s) is added to the acid(s) and the components aremixed. The acid may be present as an anion and the base may be presentas a cation (i.e. a quaternary nitrogen) in the mixture. The acid andnitrogenous base are in the form of salts or quaternary nitrogencompounds. As known by one skilled in the art, upon mixing the acid andnitrogenous base together, the nitrogenous base becomes a conjugate acidand the acid becomes a conjugate base.

The surface active agents and blends of surface active agents may beprepared in a variety of forms such as, for example, liquids, solutions,solids, powders, flakes, semi-solids, gels, “ringing” gels, G-phaseliquids, hexagonal phase solids, or thick pastes. The surface activeagents may be spray dried, flaked, extruded, and the like. Although notcritical to the present invention, the polymerizable surface activeagents may be prepared “neat” or in a conventional solvent such aswater, low molecular weight alcohol or hydrocarbon, or a mixturethereof, to produce a solution of the polymerizable surface activeagent. The present invention encompasses polymerizable surface activeagents as salts in dry form and as aqueous solutions. The polymerizablesurface active agents may be isolated by drying a solution of thesurface active agents; a solution of polymerizable surface active agentsmay be prepared by dissolving a solid form of the polymerizable surfaceactive agent (i.e. a salt) in water, low molecular weight alcohol orhydrocarbon, or a mixture thereof.

Polymerizable surface active agents of the present invention may beprepared and mixed together to produce a surface active mixturecomprising “neat” surface active agents or an aqueous surfactant blend.Additionally, neat or aqueous blends of the polymerizable surface activeagents may be prepared by contacting a blend of two or more nitrogenousbases with one acid, or by contacting a blend of two or more nitrogenousbases with a blend of 2 or more acids. Conversely, blends of thepolymerizable surface active agents may be prepared by contacting ablend of two or more acids with one nitrogenous base, or by contacting ablend of two or more acids with a blend of two or more nitrogenousbases.

The polymerizable surface active agents utilized in the presentinvention may be homopolymerized (i.e. polymerized with themselves), orpartially homopolymerized, prior to use in the polymerization, to form ahomopolymeric surface active agent or a blend of homopolymeric surfaceactive agent(s) and polymerizable surface active agents.

Further, the polymerizable surface active agents utilized in the presentinvention are also useful, for example, in detergents (e.g., laundrydetergents, dish detergents, automatic dishwasher detergents, etc.),shampoos, 2-in-1 shampoos, 3-in-1 shampoos, cleansers, soaps, liquidhand soaps, body washes, agricultural herbicide and pesticideformulations and the like.

The acids useful in the present invention are generally sulfonic acids,polysulfonic acids, sulfonic acids of oils, paraffin sulfonic acids,lignin sulfonic acids, petroleum sulfonic acids, tall oil acids, olefinsulfonic acids, hydroxyolefin sulfonic acids, polyolefin sulfonic acids,polyhydroxy polyolefin sulfonic acids, carboxylic acids, perfluorinatedcarboxylic acids, carboxylic acid sulfonates, alkoxylated carboxylicacid sulfonic acids, polycarboxylic acids, polycarboxylic acidpolysulfonic acids, alkoxylated polycarboxylic acid polysulfonic acids,phosphoric acids, alkoxylated phosphoric acids, polyphosphoric acids,and alkoxylated polyphosphoric acids, fluorinated phosphoric acids,phosphoric acid esters of oils, phosphinic acids, alkylphosphinic acids,aminophosphinic acids, polyphosphinic acids, vinyl phosphinic acids,phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters,α-phosphono fatty acids, oragnoamine polymethylphosphonic acids,organoamino dialkylene phosphonic acids, alkanolamine phosphonic acids,trialkyledine phosphonic acids, acylamidomethane phosphonic acids,alkyliminodimethylene diphosphonic acids, polymethylene-bis(nitrilodimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene) amineoxide acids, esters of substituted aminomethylphosphonic acids,phosphonamidic acids, acylated amino acids (e.g., amino acids reactedwith alkyl acyl chlorides, alkyl esters or carboxylic acids to produceN-acylamino acids), N-alkyl acylamino acids, and acylated proteinhydrolysates, and mixtures thereof.

Other acids which are useful in the present invention are selected fromthe group comprising linear or branched alkylbenzene sulfonic acids,alkyl sulfuric acid esters, alkoxylated alkyl sulfuric acid esters,α-sulfonated alkyl ester acids, α-sulfonated ester diacids, alkoxylatedα-sulfonated alkyl ester acids, α-sulfonated dialkyl diester acids,di-α-sulfonated dialkyl diester acids, α-sulfonated alkyl acetate acids,primary and secondary alkyl sulfonic acids, perfluorinated alkylsulfonic acids, sulfosuccinic mono- and diester acids, polysulfosuccinicpolyester acids, sulfoitaconic diester acids, sulfosuccinamic acids,sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids,sulfophthalic acids, sulfoisophthalic acids, phthalamic acids,sulfophthalamic acids, alkyl ketone sulfonic acids,hydroxyalkane-1-sulfonic acids, lactone sulfonic acids, sulfonic acidamides, sulfonic acid diamides, alkyl phenol sulfuric acid esters,alkoxylated alkyl phenol sulfuric acid esters, alkylated cycloalkylsulfuric acid esters, alkoxylated alkylated cycloalkyl sulfuric acidesters, dendritic polysulfonic acids, dendritic polycarboxylic acids,dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, andtauric acids, and mixtures thereof.

Additionally in accordance with the present invention, suitable acids ofthe present invention include fluorinated carboxylic acids, fluorinatedsulfonic acids, fluorinated sulfate acids, fluorinated phosphonic andphosphinic acids, and mixtures thereof.

Due to their inherent hydrolytic instability, the sulfuric acid estersare preferably immediately converted to ethylenically unsaturated aminesalts. For example, linear dodecyl alcohol is sulfated with SO₃ toproduce an intermediate, hydrolytically unstable, dodecyl alcoholsulfate acid as shown in Scheme I below. The intermediate acid isneutralized with an ethylenically unsaturated nitrogenous base, such asallyl amine, to produce a dodecyl sulfate ethylenically unsaturatedamine salt.

Scheme I: Formation of Dodecyl Sulfate Ethylenically Unsaturated AmineSalt

CH₃(CH₂)₁₁OH+SO₃→[CH₃(CH₂)₁₁OSO₃H]+H₂NCH₂CH═CH₂→[CH₃(CH₂)₁₁OSO₃]⁻[NH₃CH₂CH═CH₂]⁺

Additionally, for example, methyl laurate is sulfonated with SO₃ toproduce an intermediate α-sulfonated lauryl methyl ester acid, as shownin Scheme II below. This acid is neutralized with an ethylenicallyunsaturated nitrogenous base, such as allyl amine, to produce anα-sulfonated lauryl methyl ester ethylenically unsaturated amine salt.Additionally, an α-sulfonated lauryl methyl ester ethylenicallyunsaturated amine di-salt may be produced as shown below in Scheme III.The α-sulfonated lauryl methyl ester ethylenically unsaturated aminesalt and the α-sulfonated lauryl fatty acid ethylenically unsaturatedamine di-salt may be formed as a mixture depending on the sulfonationconditions employed. The ratio of unsaturated amine salt to unsaturatedamine di-salt is readily controlled by sulfonation conditions, wellknown to those skilled in the art.

Ethylenically unsaturated amine salts of sulfosucinnate ester acids aretypically produced by sulfitation of a succinic acid alkyl diester withsodium bisulfite, followed by, for example, ionic exchange with anethylenically unsaturated nitrogenous base, such as allyl amine, asshown in Scheme IV below.

The sarcosinic acid ethylenically unsaturated amine salts are preparedby the amidation of a fatty acid, a fatty acid alkyl ester or a fattyacid chloride with sarcosine, followed by addition of an ethylenicallyunsaturated nitrogenous base, such as allyl amine, as shown in Scheme Vbelow. Optionally, and somewhat less preferably, the ethylenicallyunsaturated nitrogenous base is combined with sarcosine to produce thecorresponding sarcosine salt, which is then be used to amidate the fattyacid, fatty acid alkyl ester or fatty acid chloride.

The isethionic acid ethylenically unsaturated amine salts may beprepared by the esterification of a fatty acid, a fatty acid alkyl esteror a fatty acid chloride with isethionic acid, followed by addition ofan ethylenically unsaturated nitrogenous base, such as allyl amine, asshown in Scheme VI below. Additionally, isethionic acid ethylenicallyunsaturated amine salts may be prepared by esterifying a fatty acid, afatty acid alkyl ester or a fatty acid chloride with the sodium salt ofisethionic acid, followed by ion exchange with the ethylenicallyunsaturated nitrogenous base, such as allyl amine. Optionally,isethionic acid, or its sodium salt, may be combined with theethylenically unsaturated nitrogenous base, such as allyl amine, toproduce the isethionic acid allyl amine salt, which may then beesterified with a fatty acid, a fatty acid alkyl ester or a fatty acidchloride.

The preferred acids of the present invention are branched or linearalkylbenzene sulfonic acids, alkyl sulfuric acid esters, alkoxylatedalkyl sulfuric acid esters, α-sulfonated alkyl ester acids, fattycarboxylic acids and phosphoric acid esters, and mixtures thereof. Themost preferred acids of the present invention are branched or linearalkylbenzene sulfonic acids, alkyl sulfuric acid esters, and alkoxylatedalkyl sulfuric acid esters, and mixtures thereof.

Other useful surfactants in accordance with the present inventioninclude sulfonic acid salts of ethylenically unsaturated amines, derivedfrom sultone precursors, such as cyclic alkyl sultones. Examples ofthese sultone-derived sulfonic acid salts (e.g., allyl amine salts)include 2-acetamidoalkyl-1-sulfonates and amino carboxy acid alkylsulfonates, as shown in Scheme VII and Scheme VIII below.

In general, nitrogenous bases, which are useful in the present inventionare any nitrogenous base which contains an ethylenically unsaturatedmoiety, including various vinyl amines. The nitrogenous base useful inaccordance with the present invention is a compound of the formula

wherein R₁, R₂ and R₃ are independently hydrogen or organic groupscontaining an ethenylene group, provided that at least one of R₁-R₃ is astraight or branched chain alkyl group containing 1-8 carbon atoms andan ethenylene functionality.

Additionally, other examples of nitrogenous bases that are useful in thepresent invention are ethylenically unsaturated amines selected from thegroup comprising vinyl amine, N-methyl N-allyl amine, C₁-C₂₄ alkyl allylamine, C₁-C₂₄ alkyl ethoxylated and/or propoxylated allyl amine, C₁-C₂₄dialkyl allyl amine, ethoxylated and/or propoxylated allyl amine diallylamine, C₁-C₂₄ alkyl diallyl amine, ethoxylated and/or propoxylateddiallyl amine, triallyl amine, 1,2-diaminoethene, aminocrotonitrile,diaminomaleonitrile, N-allylcyclopentylamine, N-allylaniline,allylcyclohexylamine,[1-(2-allylphenoxy)-3-(isopropylamino)-2-propanol],3-amino-2-butenethioamide, bis[4-(dimethylamino)benzylidene]acetone,1,4-butanediol bis(3-aminocrotonate), 3-amino-1-propanol vinyl ether,2-(diethylamino)ethanol vinyl ether, 4-(diethylamino)cinnamaldehyde,4-(diethylamino)cinnamonitrile, 2-(diethylamino)ethyl methacrylate,diethyl (6-methyl-2-pyridylaminomethylene)maleate,3-(dimethylamino)acrolein, 2-(dimethylamino)ethyl methacrylate,4-dimethylaminocinnamaldehyde, 2-(dimethylamino)ethyl acrylate,3-(dimethylamino)-2-methyl-2-propenal, 9-vinylcarbazole,N-vinylcaprolactam, 1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine,allylcyclohexylamine, N-allylcyclopentylamine,allyl(diisopropylamino)dimethylsilane, 1-allylimidazole,1-vinyl-2-pyrrolidinone, N-[3-(dimethylamino)propyl]methacrylamide,4-[4-(dimethylamino)styryl]pyridine,2-[4-(dimethylamino)styryl]pyridine,2-[4-(1,2-diphenyl-1-butenyl)phenoxy]-N,N-dimethylethylamine,2-[4-dimethylamino)styryl]-benzothiozole,5-[4-(dimethylamino)phenyl]-2,4-pentandienal,(dimethylamino-methylene)malononitrile, 4-dimethylaminocinnamonitrile,4-(dimethylamino)chalcone, [6-(3,3-dimethylallylamino-purine riboside,3,7-dimethyl-2,6-octadien-1-ylamine, 2-isopropenylaniline, isopropyl3-aminocrotonate, S-{2-[3-(hexyloxy)benzoyl]-vinyl}glutathione, methyl3-aminocrotonate, N-methylallylamine,N-methyl-1-(methylthio)-2-nitroetheneamine, oleylamine,tetrakis(dimethylamino)ethylene,5-[(6,7,8-trimethoxy-4-quinazolinyl)amino]-1-pentanol nitrate ester,tris(2-methylallyl)amine, N,N,N′,N′-tetramethyl-2-butene- 1,4-diamine,S-{2-[3-(octyloxy)benzoyl]vinyl}-glutathione,4,4′-vinylidene-(N,N-dimethylaniline), 2′,5′-dimethoxy-4-stilbenamine,3-(dimethylamino)propyl acrylate, 3-dimethylaminoacrylonitrile,4-(dimethylamino)-cinnamic acid,2-amino-1-propene-1,1,3-tricarbonitrile, 2-amino-4-pentenoic acid,N,N′-diethyl-2-butene-1,4-diamine,10,11-dihyro-N,N-dimethyl-5-methylene-5H-dibenzo[a,d]-cyclohepene-10-ethanaminemaleate,4-(dicyanomethylene)-2-methyl-6-(4-dimethyl-aminostyryl)-4H-pyran,N-ethyl-2-methylallylamine, ethyl 3-aminocrotonate,ethyl-α-cyano-3-indoleacrylate, ethyl-3-amino-4,4-dicyano-3-butenoate,1,3-divinyl-1,1,3,3-tetramethyldisilazane,N-(4,5-dihydro-5-oxo-1-phenyl-1H-pyrazol-3-yl)-9-octadecen-amide, andN-oleoyl-tryptophan ethyl ester, and mixtures thereof.

More preferred nitrogenous bases of the present invention are allylamine, diallyl amine, triallyl amine, methylallyl amine, allyldimethylamine, methyl 3-amino crotonate, 3-amino crotononitrile,3-amino-1-propanol vinyl ether, N-methyl N-allyl amine,2-(dimethylamino)ethyl acrylate, or 1,4-diamino-2-butene, and mixturesthereof. The most preferred nitrogenous bases of the present inventionare allyl amine, diallyl amine, triallyl amine, methallyl amine,N-methyl N-allyl amine, and 2-(dimethylamino)ethyl acrylate, andmixtures thereof.

Accordingly, the present invention utilizes surface active agents of theformula:

(R₁)_(n)—Ar(SO₃ ⁻M⁺)_(m)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl,polynapthyl, styryl, or polystyryl group, or a mixture thereof; whereinM⁺ is a conjugate acid of the nitrogenous base; wherein n=1-5 and m=1-8;and wherein the total number of carbon atoms represented by (R₁)_(n) isat least 5. In a preferred embodiment R₁ is a saturated or unsaturatedhydrocarbon group having from about 6-24 carbon atoms, Ar is a phenyl,M⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine or2-(dimethylamino)ethyl acrylate, and mixtures thereof and n=1 and m=1.In another preferred embodiment, the surface active agent is of theformula:

wherein n1=4-18; and wherein R′ is hydrogen or saturated or unsaturatedhydrocarbon group having from about 1-8 carbon atoms.

The present invention further utilizes surface active agents of theformula

(R₁)_(n1)-{AR(SO₃ ⁻M⁺)_(m1)}-O-{Ar(SO₃ ⁻M⁺)_(m2)}-(R₂)_(n2)

wherein R₁ and R₂ are independently hydrogen, or saturated orunsaturated hydrocarbon groups having from about 1-24 carbon atoms;wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, orpolystyryl group, or a mixture thereof; wherein M⁺ is a conjugate acidof the nitrogenous base; wherein n1 and n2 are independently 0-5,provided that n1 and n2 are not both equal to zero; and wherein m1 andm2 are independently 0-8, provided that m1 and m2 are not both equal tozero. In a preferred embodiment, R₁ is hydrogen and R₂ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, Ar isphenyl, M⁺ is a conjugate acid of the nitrogenous base, the nitrogenousbase selected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine or2-(dimethylamino)ethyl acrylate, and mixtures thereof, n1=4, n2=1, andm1 and m2 both equal one. In another preferred embodiment, R₁ and R₂ areindependently saturated or unsaturated hydrocarbon groups having fromabout 6-24 carbon atoms, Ar is phenyl, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, n1 and n2 both equal one, and m1 and m2 both equalone. In another preferred embodiment, the surface active agent is of theformula:

wherein n and n′ are independently 4-18; and wherein R′ and R″ areindependently hydrogen, methyl, ethyl or propyl.

The present invention further utilizes surface active agents of theformula:

R₁—CH(SO₃ ⁻M⁺)CO₂R₂

wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; and wherein M⁺ is aconjugate acid of the nitrogenous base. In a preferred embodiment, R₁ isa saturated or unsaturated hydrocarbon group having from about 6-24carbon atoms, R₂ is methyl, ethyl, or propyl, or a mixture thereof, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=3-18.

The present invention further utilizes surface active agents of theformula:

R₁—CH(SO₃ ^(−M+))CO₂M³⁰

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 3-24 carbon atoms; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof. In another preferred embodiment, thesurface active agent is of the formula:

wherein n=3-18.

The present invention further utilizes surface active agents of theformula:

R₁—CH(SO₃ ⁻M⁺)C(O)O(CH₂CH(R′)O)_(n)R₂

wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; wherein R′ is methyl orhydrogen; wherein n=1-100; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 4-24 carbon atoms, R′ ismethyl or hydrogen, R₂ is methyl, ethyl, or propyl, and mixturesthereof, M⁺ is a conjugate acid of the nitrogenous base, the nitrogenousbase selected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof, and n=1 -100. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18; and wherein n2=1-20.

The present invention further utilizes surface active agents of theformula:

R₁—(SO₃ ⁻M⁺)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 6-24 carbon atoms and wherein M⁺+ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=5-17.

The present invention further utilizes surface active agents of theformula:

R₁CO₂(CH₂)_(n)CH(SO₃ ⁻M⁺)CO₂R₂

wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; wherein n=0-10; and whereinM⁺ is a conjugate acid of the nitrogenous base. In a preferredembodiment, R₁ and R₂ are independently saturated or unsaturatedhydrocarbon groups having from about 1-24 carbon atoms, n=1-6, and M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof. In another preferred embodiment, thesurface active agent is of the formula:

wherein n1=0-17

The present invention further utilizes surface active agents of theformula:

R₁CO₂(CH₂)_(n)SO₃ ⁻M⁺

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein n=1-10; and wherein M⁺ is a conjugateacid of the nitrogenous base. In a preferred embodiment, R₁ is asaturated or unsaturated hydrocarbon group having from about 6-24 carbonatoms, n=1-5, and M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting essentially of allylamine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allylamine, or 2-(dimethylamino)ethyl acrylate, or a mixture thereof. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further utilizes surface active agents of theformula:

(R₁)_(n)—AR—O(CH₂CH(R′)O)_(m)(SO₃ ^(−M) ⁺)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl,polynapthyl, styryl, or polystyryl group, and mixtures thereof; whereinR′ is methyl or hydrogen; wherein M⁺ is a conjugate acid of thenitrogenous base; wherein n=1-4; wherein the total number of carbonatoms represented by (R₁)_(n) is at least 5; and wherein m=0-100. In apreferred embodiment, R₁ is a saturated or unsaturated hydrocarbon grouphaving from about 6-24 carbon atoms, Ar is phenyl; M⁺ is a conjugateacid of the nitrogenous base, the nitrogenous base selected from thegroup consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof, n=1, and m=0-100. In another preferredembodiment, the surface active agent is of the formula:

wherein n1=5-18; and wherein n2=0-20.

The present invention further utilizes surface active agents of theformula:

R₁O(CH₂CH(R′)O)_(n)(SO₃ ⁻M⁺)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; whereinn=0-100; and wherein M⁺ is a conjugate acid of the nitrogenous base. Ina preferred embodiment, R₁ is a saturated or unsaturated hydrocarbongroup having from about 6-24 carbon atoms, R′ is methyl or hydrogen,n=0-100, and M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting of allyl amine,diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,or 2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n1=5-18. In another preferred embodiment, the surface activeagent is of the formula:

wherein n1 =5-18; and wherein n=1-20.

The present invention further utilizes surface active agents of theformula:

R₁CO₂ ⁻M⁺

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 4-24 carbon atoms; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=5-18.

The present invention further utilizes surface active agents of theformula:

R₁CON(R′)(CH₂)_(n)CO₂ ⁻M⁺

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl, ethyl, propyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base; andwherein n=1-10. In a preferred embodiment, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, R′ is methyl, ethyl, propyl or hydrogen, and n=2-5. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further utilizes surface active agents of theformula:

R₁CON(R′)(CH₂)_(n)SO₃M⁺

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl, ethyl, propyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base; andwherein n=1-10. In a preferred embodiment, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, R′ is methyl, ethyl, propyl or hydrogen, and n=2-5. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further utilizes surface active agents of theformula:

R₁O(CH₂CH(R′)O)_(n)COCH₂SO₃ ⁻M⁺

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; whereinn=0-100; wherein M⁺ is a conjugate acid of the nitrogenous base. In apreferred embodiment, R₁ is a saturated or unsaturated hydrocarbon grouphaving from about 6-24 carbon atoms; R′ is methyl or hydrogen, M⁺ is aconjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof; and n=0-100. In another preferredembodiment, the surface active agent is of the formula:

wherein n1=5-17; and wherein n=0-20.

The present invention further utilizes surface active agents of theformula:

R₁O(PO₃)^(x−)M⁺ _(y)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms, phenyl, polyphenyl, napthyl, polynapthyl,styryl, or polystyryl group, an alkyl/alkoxylate substituted phenyl, analkyl/alkoxylate substituted or poly-substituted polyphenyl, analkyl/alkoxylate substituted or poly-substituted napthyl, analkyl/alkoxylate substituted or poly-substituted polynapthyl, analkyl/alkoxylate substituted or poly-substituted styryl, or analkyl/alkoxylate substituted or poly-substituted polystyryl group, andmixtures thereof; wherein M⁺ is a conjugate acid of the nitrogenousbase; wherein x=1 or 2; and wherein y=1 or 2.

The present invention further utilizes surface active agents of theformula:

[R₁O(CH₂CH(R′)O)_(m)]_(n)P(O)_(p) ^(x−)M⁺ _(y)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof; m=0-100; wherein n=1 or 2; wherein p=2or 3; wherein x=1 or 2; and wherein y=1 or 2.

The present invention further utilizes surface active agents of theformula:

[(R₁)_(n)ArO(CH₂CH(R′)O)_(m)]_(q)P(O)_(p) ^(x−)M⁺ _(y)

wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is phenyl; wherein R′ is methyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting of allyl amine,diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n=1-4;wherein m=0-100; wherein q=1 or 2; wherein p=2 or 3; wherein x=1 or 2;and wherein y=1 or 2.

The present invention further utilizes polymerizable surface activeagents which are quaternary ammonium salts of the general formula:

wherein R₁, R₂, R₃, and R₄ are independently, substituted orunsubstituted hydrocarbyl groups of from about 1 to about 30 carbonatoms, or hydrocarbyl groups having from about 1 to about 30 carbonatoms and containing one or more aromatic, ether, ester, amido, or aminomoieties present as substituents or as linkages in the radical chain,wherein at least one of the R₁-R₄ groups contains at least one or moreethenylene groups; and wherein X⁻ is an anion group selected from thegroup consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate,carboxylate, nitrate, and acetate. Additionally, useful polymerizablesurface active agents include those of the above general formula in theform of ring structures formed by covalently linking two of the R₁-R₄groups. Examples include unsaturated imidazolines, imidazoliniums, andpyridiniums, and the like. These quaternary ammonium salts may beprepared by a variety of methods known to the art, for example, halideexchange, wherein a halide based quaternary ammonium compound is ionexchanged with X⁻, where X⁻ is defined above.

The present invention encompasses amine oxide-derived polymerizablesurface active agents, formed as shown in Scheme IX, wherein R₁, R₂, R₃are independently, substituted or unsubstituted hydrocarbyl groups offrom about 1 to about 30 carbon atoms, or hydrocarbyl groups having fromabout 1 to about 30 carbon atoms and containing one or more aromatic,ether, ester, amido, or amino moieties present as substituents or aslinkages in the radical chain, wherein at least one of the R₁-R₃ groupscontains at least one or more ethenylene groups; and wherein X⁻ is ananion group selected from the group consisting of sulfonate, sulfate,sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.Additionally, useful polymerizable surface active agents include thoseof the above general formula in the form of ring structures formed bycovalently linking two of the R₁-R₄ groups. Examples include unsaturatedimidazolines, imidazoliniums, and pyridiniums, and the like.

The present invention further encompasses quaternary halide-derivedpolymerizable surface active agents, formed as shown in Scheme X,wherein R₁, R₂, R₃ are independently, substituted or unsubstitutedhydrocarbyl groups of from about 1 to about 30 carbon atoms, orhydrocarbyl groups having from about 1 to about 30 carbon atoms andcontaining one or more aromatic, ether, ester, amido, or amino moietiespresent as substituents or as linkages in the radical chain, wherein atleast one of the R₁-R₃ groups contains at least one or more ethenylenegroups; and wherein X⁻ is an anion group selected from the groupconsisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate,carboxylate, nitrate, and acetate. Additionally, useful polymerizablesurface active agents include those of the above general formula in theform of ring structures formed by covalently linking two of the R₁-R₄groups. Examples include unsaturated imidazolines, imidazoliniums, andpyridiniums, and the like.

The present invention further encompasses polymerizable onium compounds,particularly ammonium salts, sulfonium salts, sulfoxonium salts, oxoniumsalts, nitronium salts, and phosphonium salts of various anions,including for example, anions group selected from the group consistingof sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate,nitrate, acetate and various halides; wherein the onium compoundcontains at least one ethenylene functionality.

“Reverse” Polymerizable Surface Active Agents

Although somewhat less preferred, the polymerizable, surface activeagents utilized in the present invention may be “reverse” polymerizablesurface active agents. Reverse polymerizable surface active agentsutilized in the present invention are salts or quaternary nitrogencompounds comprising: (1) at least one ethylenically unsaturated acid,wherein the acid contains at least one ethylenically unsaturated moietyand is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or amixture thereof; and (2) at least one substantially saturatednitrogenous base, wherein the nitrogenous base contains at least onenitrogen atom and a C₁-C₂₄ alkyl group. By substantially saturatednitrogenous base, it is meant that the nitrogenous base contains lessthan about 5% unsaturation in the alkyl group(s).

In general, the ethylenically unsaturated acids of the present inventionare any sulfonic acids, carboxylic acids, or phosphoric acids whichcontain at least one unsaturated moiety. More specifically, theethylenically unsaturated acids useful in the present invention aregenerally vinyl sulfonic acids, vinyl sulfinic acids, vinyl sulfenicacids, vinyl sulfonic acid esters, vinyl carboxylic acids, vinyl,phosphoric acids, vinyl phosphonic acids, vinyl phosphinic, vinylphosphenic acids, unsaturated sulfonic acids, unsaturated polysulfonicacids, unsaturated sulfonic acids of oils, unsaturated paraffin sulfonicacids, unsaturated lignin sulfonic acids, unsaturated petroleum sulfonicacids, unsaturated tall oil acids, unsaturated olefin sulfonic acids,unsaturated hydroxyolefin sulfonic acids, unsaturated polyolefinsulfonic acids, unsaturated polyhydroxy polyolefin sulfonic acids,unsaturated carboxylic acids, unsaturated perfluorinated carboxylicacids, unsaturated carboxylic acid sulfonates, unsaturated alkoxylatedcarboxylic acid sulfonic acids, unsaturated polycarboxylic acids,unsaturated polycarboxylic acid polysulfonic acids, unsaturatedalkoxylated polycarboxylic acid polysulfonic acids, unsaturatedphosphoric acids, unsaturated alkoxylated phosphoric acids, unsaturatedpolyphosphoric acids, and unsaturated alkoxylated polyphosphoric acids,unsaturated fluorinated phosphoric acids, unsaturated phosphoric acidesters of oils, unsaturated phosphinic acids, unsaturatedalkylphosphinic acids, unsaturated aminophosphinic acids, unsaturatedpolyphosphinic acids, unsaturated vinyl phosphinic acids, unsaturatedphosphonic acids, unsaturated polyphosphonic acids, unsaturatedphosphonic acid alkyl esters, unsaturated o-phosphono fatty acids,unsaturated oragnoamine polymethylphosphonic acids, unsaturatedorganoamino dialkylene phosphonic acids, unsaturated alkanolarninephosphonic acids, unsaturated trialkyledine phosphonic acids,unsaturated acylamidomethane phosphonic acids, unsaturatedalkyliminodimethylene diphosphonic acids, unsaturatedpolymethylene-bis(nitrilodimethylene)tetraphosphonic acids, unsaturatedalkyl bis(phosphonoalkylidene) amine oxide acids, unsaturated esters ofsubstituted aminomethylphosphonic acids, unsaturated phosphonamidicacids, unsaturated acylated amino acids (e.g., amino acids reacted withalkyl acyl chlorides, alkyl esters or carboxylic acids to produceN-acylamino acids), unsaturated N-alkyl acylamino acids, and unsaturatedacylated protein hydrolysates, and mixtures thereof.

Other ethylenically unsaturated acids which are useful in the presentinvention are selected from the group comprising unsaturated linear orbranched alkylbenzene sulfonic acids, unsaturated alkyl sulfuric acidesters, unsaturated alkoxylated alkyl sulfuric acid esters, unsaturatedα-sulfonated alkyl ester acids, unsaturated α-sulfonated ester diacids,unsaturated alkoxylated α-sulfonated alkyl ester acids, unsaturatedα-sulfonated dialkyl diester acids, unsaturated di-α-sulfonated dialkyldiester acids, unsaturated α-sulfonated alkyl acetate acids, unsaturatedprimary and secondary alkyl sulfonic acids, unsaturated perfluorinatedalkyl sulfonic acids, unsaturated sulfosuccinic mono- and diester acids,unsaturated polysulfosuccinic polyester acids, unsaturated sulfoitaconicdiester acids, unsaturated sulfosuccinamic acids, unsaturatedsulfosuccinic amide acids, unsaturated sulfosuccinic imide acids,unsaturated phthalic acids, unsaturated sulfophthalic acids, unsaturatedsulfoisophthalic acids, unsaturated phthalamic acids, unsaturatedsulfophthalamic acids, unsaturated alkyl ketone sulfonic acids,unsaturated hydroxyalkane-1-sulfonic acids, unsaturated lactone sulfonicacids, unsaturated sulfonic acid amides, unsaturated sulfonic aciddiamides, unsaturated alkyl phenol sulfuric acid esters, unsaturatedalkoxylated alkyl phenol sulfuric acid esters, unsaturated alkylatedcycloalkyl sulfuric acid esters, unsaturated alkoxylated alkylatedcycloalkyl sulfuric acid esters, unsaturated dendritic polysulfonicacids, unsaturated dendritic polycarboxylic acids, unsaturated dendriticpolyphosphoric acids, unsaturated sarcosinic acids, unsaturatedisethionic acids, and unsaturated tauric acids, and mixtures thereof.

Additionally in accordance with the present invention, suitableethylenically unsaturated acids of the present invention includeunsaturated fluorinated carboxylic acids, unsaturated fluorinatedsulfonic acids, unsaturated fluorinated sulfate acids, unsaturatedfluorinated phosphonic and phosphinic acids, and mixtures thereof.

In general, the substantially saturated nitrogenous bases of the presentinvention are any bases which contain at least one nitrogen atom, andare capable of forming a salt with the ethylenically unsaturated acid.The saturated nitrogenous bases suitable for use in the presentinvention include any primary, secondary or tertiary amine, which has atleast one C₁-C₂₄ alkyl group. Preferably, the alkyl groups of suchamines have from about 12 to about 22 carbon atoms, and may besubstituted or unsubstituted. Such amines, include for example,stearamido propyl dimethyl amine, diethyl amino ethyl stearamide,dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine,tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated(5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, andarachidylbehenylamine and mixtures thereof.

Auxiliary Polymerizable Surface Active Agents

The present invention encompasses the use of auxiliary polymerizablesurface active agents, i.e. polymerizable surface active agent known tothose skilled in the art, in combination with the polymerizable surfaceactive agents, homopolymeric surface active agents, and supplementalsurface active agents described herein. Examples of auxiliarypolymerizable surface active agents useful in the present invention areshown below in Table I.

TABLE I Auxillary Polymerizable Surface Active Agents Diallyl AminePluronics - BASF

Linoleic Alcohol Derivatives - ICI

Allyl Alkyl Phenol Derivatives - DKS (Japan)

Acrylate Derivatives - PPG

Allyl Alcohol Alkenyl Succinic Anhydride Derivatives - KAO (Japan)

Polystep RA Series (Maleic Derivatives) - Stepan Co.

Maleic Derivatives - Rhone Poulenc

Trem LF-40 Allyl Sulfosuccinate Derivatives - Henkel

Additional auxiliary polymerizable surfactants useful herein, forexample, are generally disclosed in Polymerizable Surfactants Guyot, A.Current Opinions in Colloid and Surface Science, 1996, pg. 580-585;Reactive Surfactants in Emulsion Polymerization Guyot, A.; et. al;Advances in Polymer Science, Vol. 11, Springer-Verlag, Berlin, 1994,pg.43-65; and Polymerizable Surfactant Holmber, K. Progress in OrganicCoatings, 20 (1992) 325-337 (all incorporated herein in their entirety).

Supplemental Surface Active Agents

Generally, it is advantageous to not use conventional, non-polymerizablesurface active agents in the present invention. However, if so desired,the polymerizable surface active agents of the present invention may beused in the polymerization in combination with minor amounts of aconventional polymerization surfactants, i.e. supplemental surfaceactive agents, that are not polymerizable. Without being bound by anyparticular theory, these supplemental surface active agents may allowfor the varying of particle size of the resulting discrete, solid,polymeric particles. The supplemental surface active agents aregenerally anionic, nonionic, cationic or amphoteric surfactants ormixtures thereof, and are typically used as in a concentration of about0.01 to about 20.0 percent by weight, based on the total weight ofsurface active agents (i.e. both polymerizable and non-polymerizable).Somewhat more preferably, the supplemental surface active agents areused in a concentration of about 0.01 to about 5.0 percent by weight,based on the total weight of supplemental surface active agents (i.e.both polymerizable and non-polymerizable).

Suitable supplemental nonionic surface active agents are generallydisclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30,1975, at column, 13 line 14 through column 16, line 6, incorporatedherein by reference. Generally, the supplemental nonionic surface activeagent is selected from the group comprising polyoxyethylenatedalkylphenols, polyoxyethyleneated straight chain alcohols,polyoxyethyleneated branched chain alcohols, polyoxyethyleneatedpolyoxypropylene glycols, polyoxyethyleneated mercaptans, fatty acidesters, glyceryl fatty acid esters, polyglyceryl fatty acid esters,propylene glycol esters, sorbitol esters, polyoxyethyleneated sorbitolesters, polyoxyethylene glycol esters, polyoxyethyleneated fatty acidesters, primary alkanolamides, ethoxylated primary alkanolamides,secondary alkanolamides, ethoxylated secondary alkanolamides, tertiaryacetylenic glycols, polyoxyethyleneated silicones, N-alkylpyrrolidones,alkylpolyglycosides, alkylpolylsaccharides, EO-PO block polymers,polyhydroxy fatty acid amides, amine oxides and mixtures thereofFurther, exemplary, non-limiting classes of useful supplemental nonionicsurface active agents are listed below:

1. The polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. In general, the polyethylene oxide condensates arepreferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atomsin either a straight or branched chain configuration with the alkyleneoxide. In a preferred embodiment, the ethylene oxide is present in anamount equal to from about 1 to about 25 moles of ethylene oxide permole of alkyl phenol. Commercially available nonionic surfactants ofthis type include Igepal® CO-630, marketed by Stepan Company, Canada;and Triton® X-45, X-114, X-100 and X-102, all marketed by the UnionCarbide Company.

2. The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contain from about 8 to about 22 carbon atoms. Particularlypreferred are the condensation products of alcohols having an alkylgroup containing from about 6 to about 11 carbon atoms with from about 2to about 10 moles of ethylene oxide per mole of alcohol. Examples ofcommercially available nonionic surfactants of this type includeTergitol® 15-S-9 (the condensation products of C₁₁-C₁₅ linear alcoholwith 9 moles of ethylene oxide), Tergitol® 24-L-6 NMW (the condensationproducts of C₁₂-C₁₄ primary alcohol with 6 moles of ethylene oxide witha narrow molecular weight distribution), both marketed by Union CarbideCorporation; Neodol® 91-8 (the condensation product of C₉-C₁₁ linearalcohol with 8 moles of ethylene oxide), Neodol® 23-6.5 (thecondensation product of C₁₂-C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol® 91-6 (thecondensation product of C₉-C₁₁ linear alcohol with 6 moles of ethyleneoxide), marketed by Shell Chemical Company, and Kyro® EOB (thecondensation product of C₁₃-C₁₅ linear alcohol with 9 moles of ethyleneoxide), marketed by the Procter and Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds preferably has a molecular weightof from about 1500 to about 1880 and exhibits water insolubility. Theaddition of polyoxyethylene moieties to this hydrophobic portion tendsto increase the water solubility of the molecule as a whole, and theliquid character of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially available Pluronic® surfactants, marketed byBASF.

4. The condensation products of ethylene oxide with the productresulting from the reaction of propylene oxide and ethylenediamine. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, and generally has amolecular weight of from about 2500 to about 3000. This hydrophobicmoiety is condensed with ethylene oxide to the extent that thecondensation product contains from about 40% to about 80% by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic® compounds, marketed by BASF.

5. Semi-polar nonionic surfactants are a special category ofsupplemental nonionic surface active agents which include water-solubleamine oxides containing on alkyl moiety of from about 10 to about 18carbon atoms and 2 moieties selected from the group comprising alkylgroups and hydroxyalkyl groups containing from about 1 to about 3 carbonatoms; and water-soluble sulfoxides containing alkyl moieties of fromabout 10 to about 18 carbon atoms and a moiety selected from the groupcomprising alkyl groups and hydroxyalkyl groups of from about 1 to about3 carbon atoms.

6. Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Lenado,issued Jan. 21, 1986, incorporated herein by reference, having ahydrophobic group containing from about 6 to about 30 carbon atoms,preferably from about 10 to about 16 carbon atoms and a polysaccharide,e.g., a polyglucoside, hydrophilic group containing from about 1.3 toabout 10, preferably from about 1.3 to about 3, most preferably fromabout 1.3 to about 2.7 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6- positions on the preceding saccharide units.

7. An ethyl ester ethoxylate and/or alkoxylate such as those describedin U.S. Pat. No. 5,220,046, incorporated herein by reference. Thesematerial may be prepared according to the procedure set forth inJapanese Kokai patent application No. HEI 5 [1993]-222396. For example.they may be prepared by a one-step condensation reaction between analkyl ester and an alkylene oxide in the present of a catalytic amountof magnesium together with another ion selected from the group of Al⁺³,Ga⁺³, In⁺³, Co⁺³, Sc⁺³, La⁺³ and Mn⁺³. Optionally, and less desirably,there can be a polyalkyleneoxide chain joining the hydrophobic moietyand the polysaccharide moiety. The preferred alkyleneoxide is ethyleneoxide. Typical hydrophobic groups include alkyl groups, either saturatedor unsaturated, branched or unbranched, containing from about 8 to about18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3,preferably 2; t is from about 0 to about 10, preferably 0; and x is fromabout 1.3 to about 10, preferably from about 1.3 to 3, most preferablyfrom about 1.3 to about 2.7. The glycosyl is preferably derived fromglucose. To prepare these compounds, the alcohol or alkylpolyethoxyalcohol is formed first and then reacted with glucose, or a source ofglucose, to form the glucoside (attachment at the 1-position). Theadditional glucosyl units can then be attached between their 1-positionand the preceding glycosyl units 2-, 3-, 4-, and/or 6-position,preferably predominately the 2-position.

Examples of suitable supplemental amphoteric surface active agents areselected from the group comprising alkyl glycinates, propionates,imidazolines, amphoalkylsulfonates sold as “Miranol”® by Rhone Poulenc,N-alkylaminopropionic acids, N-alkyliminodipropionic acids, imidazolinecarboxylates, N-alkylbetaines, amido propyl betaines, sarcosinates,cocoamphocarboxyglycinates, amine oxides, sulfobetaines, sultaines andmixtures thereof. Additional suitable amphoteric surfactants includecocoamphoglycinate, cocoamphocarboxyglycinate,lauramphocarboxyglycinate, cocoamphopropionate, lauramphopropionate,stearamphoglycinate, cocoamphocarboxy-propionate, tallowamphopropionate,tallowamphoglycinate, oleoamphoglycinate, caproamphoglycinate,caprylamphopropionate, caprylamphocarboxyglycinate, cocoyl imidazoline,lauryl imidazoline, stearyl imidazoline, behenyl imidazoline,behenylhydroxyethyl imidazoline, caprylamphopropylsulfonate,cocamphopropylsulfonate, stearamphopropyl-sulfonate,oleoamphopropylsulfonate and the like.

Examples of supplemental amine oxide surface active agents which aregenerally suitable for use in the present invention are alkylamine andamidoamine oxides. Examples of supplemental betaine and sultaine surfaceactive agents which are suitable for use in the present invention arealkyl betaines and sultaines sold as “Mirataine”® by Rhone Poulenc,“Lonzaine”® by Lonza, Inc., Fairlawn, N.J. Examples of supplementalbetaines and sultaines are cocobetaine, cocoamidoethyl betaine,cocoamidopropyl betaine, lauryl betaine, lauramidopropyl betaine,palmamidopropyl betaine, stearamidopropyl betaine, stearyl betaine,coco-sultaine, lauryl sultaine, tallowamidopropyl hydroxysultaine andthe like.

Examples of supplemental cationic surface active agents useful in thepresent invention are fatty amine salts, fatty diamine salts, polyaminesalts, quaternary ammonium compounds, polyoxyethyleneated fatty amines,quatemized polyoxyethyleneated fatty amines, amine oxides and mixturesthereof.

Examples of suitable supplemental cationic surface active agents aredisclosed in the following documents, all incorporated by referenceherein: M. C. Publishing Co., McCutcheon's Detergents & Emulsifiers,(North American Ed., 1993); Schwartz et al., Surface Active Agents,Their Chemistry and Technology, New York; Interscience Publisher, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983.

Examples of supplemental cationic surface active agents in the form ofquaternary ammonium salts include dialkyldiethyl ammonium chlorides andtrialkyl methyl ammonium chlorides, wherein the alkyl groups have fromabout 12 to about 22 carbon atoms and are derived from long-chain fattyacids, such as hydrogenated tallow fatty acid (tallow fatty acids yieldquaternary compounds wherein R₁ and R₂ have predominately from about 16to about 18 carbon atoms). Examples of supplemental quaternary ammoniumsalts useful herein include ditallowdimethyl ammonium chloride,ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammoniumchloride, di-(hydrogenated tallow)dimethyl ammonium chloride,dioctadecyl dimethyl ammonium chloride, dicicosyl dimethyl ammoniumchloride, didocosyl dimethyl ammonium chloride, di-(hydrogenatedtallow)dimethyl ammonium acetate, dihexadecyl dimethyl ammoniumchloride, dihexadecyl dimethyol ammonium acetate, ditallow dipropylammonium phosphate, ditallow dimethyl ammonium nitrate,di-(coconutalkyl)dimethyl ammonium chloride, and stearyl dimethyl benzylammonium chloride.

Salts of primary, secondary and tertiary fatty amines are also suitablesupplemental cationic surface active agents. The alkyl groups of suchsupplemental amines preferably have from about 12 to about 22 carbonatoms, and may be substituted or unsubstituted. Such amines, usefulherein, include stearamido propyl dimethyl amine, diethyl amino ethylstearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristylamine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine,ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine,and arachidylbehenylamine. Suitable supplemental amine salts include thehalogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfatesalts. Such supplemental salts include stearylamine hydrogen chloride,soyamine chloride, stearylamine formate, N-tallowpropane diaminedichloride and stearamidopropyl dimethylamine citrate. Supplementalcationic amine surfactants included among those useful in the presentinvention are also disclosed in U.S. Pat. No. 4,275,055, Nachtigal, etal., issued Jun. 23, 1981, incorporated herein by reference.

Supplemental cationic surface active agents which are especially usefulare quaternary ammonium or amino compounds having at least one N-radicalcontaining one or more nonionic hydrophilic moieties selected from thegroup comprising alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, andalkylester moieties, and combinations thereof. The compounds contain atleast one hydrophilic moiety within 4, preferably within 3, carbon atoms(inclusive) of the quaternary nitrogen or cationic amino nitrogen.Additionally, carbon atoms that are part of a hydrophilic moiety, e.g.,carbon atoms in a hydrophilic polyoxyalkylene (e.g., —CH₂—CH₂—O—), thatare adjacent to other hydrophilic moieties are not counted whendetermining the number of hydrophilic moieties within 4, or preferably3, carbon atoms of the cationic nitrogen. In general, the alkyl portionof any hydrophilic moiety is preferably a C₁-C₃ alkyl. Suitablehydrophile-containing radicals include, for example, ethoxy, propoxy,polyoxyethylene, polyoxypropylene, ethylamido, propylamido,hydroxymethyl, hydroxyethyl, hydroxypropyl, methyl ester, ethyl ester,propyl ester, or mixtures thereof, as nonionic hydrophile moieties.

Among the supplemental cationic surface active agents useful herein arethose of the general formula:

wherein R₁, R₂, R₃, and R₄ comprise, independently, substituted orunsubstituted substantially saturated hydrocarbyl chains of from about 1to about 30 carbon atoms, or a hydrocarbyl having from about 1 to about30 carbon atoms and containing one or more aromatic, ether, ester,amido, or amino moieties present as substituents or as linkages in theradical chain, wherein at least on of the R₁-R₄ groups contains one ormore hydrophilic moieties selected from the group comprising alkoxy(preferably C₁-C₃ alkoxy), polyoxyalkylene (preferably C₁-C₃polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester and combinationthereof. Preferably, the cationic conditioning surfactant contains fromabout 2 to about 10 nonionic hydrophile moieties located within theabout stated ranges. For purposes herein, each hydrophilic amido,alkoxy, hydroxyalkyl, alkylester, alkylamido or other unit is consideredto be a distinct nonionic hydrophile moiety. X⁻ is a substantiallysaturated soluble salt forming anion preferably selected from the groupcomprising halogens (especially chlorine), acetate, phosphate, nitrate,sulfonate, and alkyl sulfate radicals.

Preferred supplemental cationic surface active agents includepolyoxyethylene (2) stearyl methyl ammonium chloride, methylbis-(hydrogenated tallowamidoethyl) 2-hydroxyethyl ammonium methylsulfate, polyoxypropylene (9) diethyl methyl ammonium chloride,tripolyoxyethylene (total PEG-10) stearyl ammonium phosphate,bis-(N-hydroxyethyl-2-oleyl imidazolinium chloride)polyethylene glycol(1), and isododecylbenzyl triethanolammonium chloride.

Other supplemental ammonium quaternary and amino surface active agentsinclude those of the above general formula in the form of ringstructures formed by covalently linking two of the radicals. Examplesinclude imidazolines, imidazoliniums, and pyridiniums, etc., whereinsaid compound has at least one nonionic hydrophile-containing radical asset forth above. Specific examples include2-heptadecyl-4,5-dihydro-1H-imidazol-1-ethanol,4,5-dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl-1-phenylmethylimidazoliumchloride, and1-[2-oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]amino]ethyl]pyridiniumchloride.

Salts of primary, secondary and tertiary fatty amines are also preferredsupplemental cationic surfactant materials. The alkyl groups of suchamines preferably have from about 1 to about 30 carbon atoms and mustcontain at least one, preferably about 2 to about 10, nonionichydrophilic moieties selected from the group comprising alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester groups, andmixtures thereof.

The supplemental anionic surface active agents suitable for use in thepresent invention are generally the sodium, potassium, calcium, ammoniumor alkanolamine salts of any substantially saturated sulfonic acid,carboxylic acid, or phosphoric acid, or a mixture thereof Morespecifically, supplemental anionic surface active agents suitable foruse in the present invention are generally the sodium, potassium,calcium, ammonium or alkanolamine salts of saturated sulfonic acids,sulfinic acids, sulfenic acids, sulfonic acid esters, carboxylic acids,phosphonic acids, phosphinic, phosphenic acids, polysulfonic acids,sulfonic acids of oils, paraffin sulfonic acids, lignin sulfonic acids,petroleum sulfonic acids, tall oil acids, olefin sulfonic acids,hydroxyolefin sulfonic acids, polyolefin sulfonic acids, polyhydroxypolyolefin sulfonic acids, carboxylic acids, perfluorinated carboxylicacids, carboxylic acid sulfonates, alkoxylated carboxylic acid sulfonicacids, polycarboxylic acids, polycarboxylic acid polysulfonic acids,alkoxylated polycarboxylic acid polysulfonic acids, phosphoric acids,alkoxylated phosphoric acids, polyphosphoric acids, and alkoxylatedpolyphosphoric acids, fluorinated phosphoric acids, phosphoric acidesters of oils, phosphinic acids, alkylphosphinic acids, aminophosphinicacids, polyphosphinic acids, vinyl phosphinic acids, phosphonic acids,polyphosphonic acids, phosphonic acid alkyl esters, α-phosphono fattyacids, oragno amine polymethylphosphonic acids, organo amino dialkylenephosphonic acids, alkanolamine phosphonic acids, trialkyledinephosphonic acids, acylamidomethane phosphonic acids,alkyliminodimethylene diphosphonic acids,polymethylene-bis(nitrilodimethylene)tetraphosphonic acids, alkylbis(phosphonoalkylidene)amine oxide acids, esters of substitutedaminomethylphosphonic acids, phosphonamidic acids, acylated amino acids(e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters orcarboxylic acids to produce N-acylamino acids), N-alkyl acylamino acids,and acylated protein hydrolysates, and mixtures thereof.

Other supplemental anionic surface active agents suitable for use in thepresent invention are the sodium, potassium, calcium, ammonium oralkanolamine salts of saturated linear or branched alkylbenzene sulfonicacids, alkyl sulfuric acid esters, alkoxylated alkyl sulfuric acidesters, ac-sulfonated alkyl ester acids, α-sulfonated ester diacids,alkoxylated α-sulfonated alkyl ester acids, α-sulfonated dialkyl diesteracids, di-α-sulfonated dialkyl diester acids, α-sulfonated alkyl acetateacids, primary and secondary alkyl sulfonic acids, perfluorinated alkylsulfonic acids, sulfosuccinic mono- and diester acids, polysulfosuccinicpolyester acids, sulfoitaconic diester acids, sulfosuccinamic acids,sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids,sulfophthalic acids, sulfoisophthalic acids, phthalamic acids,sulfophthalamic acids, alkyl ketone sulfonic acids,hydroxyalkane-1-sulfonic acids, lactone sulfonic acids, sulfonic acidamides, sulfonic acid diamides, alkyl phenol sulfuric acid esters,alkoxylated alkyl phenol sulfuric acid esters, alkylated cycloalkylsulfuric acid esters, alkoxylated alkylated cycloalkyl sulfuric acidesters, dendritic polysulfonic acids, dendritic polycarboxylic acids,dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, andtauric acids, and mixtures thereof.

Additionally in accordance with the present invention, supplementalanionic surface active agents suitable for use in the present inventionare generally the sodium, potassium, calcium, ammonium or alkanolaminesalts of saturated fluorinated carboxylic acids, fluorinated sulfonicacids, fluorinated sulfate acids, fluorinated phosphonic and phosphinicacids, and mixtures thereof.

In a preferred embodiment of the present invention, the polymerizationprocess is conducted in the absence of any non-polymerizable,supplemental surfactant, as the polymerizable surface active agents ofthe present invention display excellent capacity for producing emulsionstability characteristics in an emulsion polymerization.

In another embodiment of the present invention, the polymerizablesurface active agents of the present invention may be used asco-monomers with the ethylenically unsaturated monomer(s) to modify thephysical properties of the resulting polymer. In this embodiment,supplemental surface active agents also may be used as additives to thepolymerization, e.g., in amounts of from about 3 to 6 weight percent,based on the total weight of monomer. Although somewhat less preferred,in a further embodiment of the present invention, any conventionalorganic solvent, which may be a solvent for both the monomer(s) and/orpolymer, or just the monomer(s) may be used.

Initiators and Additives

Organic or inorganic initiators may be used to initiate thepolymerization reaction. A sufficient quantity of a polymerizationinitiator (such as a conventional free radical initiator) is typicallyintroduced into the polymerization medium to cause polymerization of themonomer(s) at the particular temperatures employed. Initiators used inpolymerization processes may be of the type which produce free radicalsand conveniently are peroxygen compounds, for example: inorganicperoxides such as hydrogen peroxide and inorganic persulfate compoundssuch as ammonium persulfate, sodium persulfate and potassiumper-sulfate; organic hydroperoxides such as cumene hydroperoxide andtertiary butyl hydroperoxide; organic peroxides such as benzoylperoxide, acetyl peroxide, lauroyl peroxide, peroxydicarbonate esterssuch as diisopropyl peroxydicarbonate, peracetic acid and per-benzoicacid, sometimes activated by water-soluble reducing agents such asferrous compounds, sodium bisulfite or hydroxylamine hydrochloride, andother free radical producing materials such as2,2′-azobisisobutyronitrile.

A further additive which may be added to the mixture contents is aconventional chain transfer agent, such as an alkyl polyhalide ormercaptan. Examples of suitable chain transfer agents include bromoform,carbon tetrachloride, carbontetrabromide, bromoethane, C₁-C₁₂ alkylmercaptans, e.g., dodecylmercaptan, thiophenol, and hydroxyalkylmercaptans, e.g., mercaptoethanol.

All documents, e.g., patents and journal articles, cited above or beloware hereby incorporated by reference in their entirety.

In the following examples, all amounts are stated in percent by weightunless indicated otherwise.

One skilled in the art will recognize that modifications may be made inthe present invention without deviating from the spirit or scope of theinvention. The invention is illustrated further by the followingexamples which are not to be construed as limiting the invention orscope of the specific procedures or compositions described herein. Alldocuments, e.g., patents and journal articles, cited above or below arehereby incorporated by reference in their entirety.

As used in the Examples appearing below, the following designations,symbols, terms and abbreviations have the indicated meanings:

Material Definition Polystep ® A-13 Linear dodecylbenzene sulfonic acid(commercially available from Stepan Company, Northfield Illinois)Polystep ® A-16 Branched dodecylbenzene sulfonic acid, sodium salt(commercially available from Stepan Company, Northfield Illinois)Polystep ® A-17 Branched dodecylbenzene sulfonic acid (commerciallyavailable from Stepan Company, Northfield Illinois) Cedephos CP-610Nonyl Phenol 9-EO Phosphoric Acid Ester (commercially available fromStepan Company, Northfield Illinois)

The amount of agglomerated polymers, or “coagulum”, in the resultinglattices at the conclusion of the polymerization is determined bycollecting the agglomerated polymers using a 20 mesh screen that hasopenings sufficiently large enough to allow the discrete unagglomeratedpolymers to pass, rinsing the collected agglomerated polymers withwater, and weighting the remaining agglomerated polymers trapped on thescreen. The percent coagulum is calculated by dividing the weight of thecoagulum by the theoretical weight of the entire latex based upon theweights of the ingredients used for the polymerization reaction.

The viscosity of the resulting lattices following polymerization isdetermined by using a RV Brookfield synchro-lechtric viscometer equippedwith a No. 3 spindle. During such determinations 950 ml of each latex isplaced in a 1000 ml beaker and the viscometer operated at 25° C. and 60rpm.

The mechanical stability of the lattices following exposure tomechanical stress is evaluated to determine the extent to which there isa change in the viscosity and/or the visual presence of coagulum. Morespecifically, two cups of each latex are placed in a five-cup stainlesssteel Hamilton Beach blender, and the blender operated at medium speeduntil the latex coagulates. Failure of the latex is the point at whichcoagulum separation can be visually observed; a longer time of blendingat medium speed without coagulum separation, i.e. a longer time beforefailure, is a highly desirable characteristic of a latex.

Solids of lattices were determined by concentrating the latex at 120° C.in an oven to remove all volitiles, and subsequently weighing theresidue. The pH of each solution was measured using an Orion 210 pHmeter. Particle size was measured using a Nicomp 370, [submicronanalyzer, (up to 2 microns)].

The particle size of the resulting lattices is determined with a NICOMP370C Auto-dilution particle size analyzer using standard methods andprocedures for operation of such equipment and such data recorded for50% volume in units of nano-meters.

The water sensitivity, e.g. hydrophobicity, of the resulting latticeswas determined by ASTM D724-45.

All ¹H NMR spectra were recorded using a 270 MHz Joel Delta NMR FourierTransform Spectrometer. Chemical shifts (δ) are reported in parts permillion (ppm) down field from tetramethylsilane (TMS) using internal TMSor residual non-deuterated solvent as a reference. NMR data for allsamples was acquired by dissolving the solid sample in CD₃OD.

The allylamine and propyl amine may be obtained from Aldrich ChemicalCompany (USA).

In the following examples, all amounts are stated in percent by weightof active material unless indicated otherwise. One skilled in the artwill recognize that modifications may be made in the present inventionwithout deviating from the spirit or scope of the invention. Theinvention is illustrated further by the following examples which are notto be construed as limiting the invention or scope of the specificprocedures or compositions described herein.

EXAMPLE 1

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA)co-polymer (in a weight ratio of about 48:49:3), in combination with theallylamine salt of dodecylbenzenesulfonic acid (ADDBS), is prepared asfollows. About 254 g of deionized water and about 10.6 g of ADDBS (as a22% active aqueous solution), are placed in a reactor suitable foremulsion polymerization, equipped with agitation means, heating meansand cooling means. With agitation, the reactor is purged with nitrogen(99% pure), and heated to about 80-82° C. The temperature of the reactorcontents is adjusted to about 77-79° C., and about 75 g of the monomermixture (20% of a total of 374 g of the MMA/BA/MMA monomer mixture inthe ratio above) is added to the reactor. After 10 minutes, 16.9 g of asolution of ammonium persulfate (20% of the total solution of 1.9 g ofammonium persulfate dissolved in 82.5 g of water) is added to thereactor over a period of about 7 minutes with continued agitation,during which time there is an exotherm of about 7-10° C. After theexotherm is complete, about 299 g of the monomer mixture (the remaining80% MMA/BA/MMA monomer mixture), 64.5 g of the ammonium persulfatesolution (the remaining 80%), and 15.55 g of ADDBS (as the 22% activeaqueous solution) are simultaneously charged to the reactor over aperiod of 2 hours with continued agitation, while keeping the reactorcontents at a temperature of about 78-81° C. The reactor temperature isthen elevated to about 82-84° C. with continued agitation, for about 15minutes. After this 15 minute period, the reactor is cooled to about 30°C. The resulting latex product is completely removed from the reactorand gravity filtered using a first 20 mesh screen and then a second 250mesh screen. The total latex coagulum (i.e. solids) from both meshscreens is collected, combined and weighed. Various physiochemicalproperties of the latex are reported in Table II.

FIG. 1 depicts the partial ¹H NMR spectrum, showing the region of δ5.0-8.0, of the allylamine salt of dodecylbenzenesulfonic acid (ADDBS).The peaks centered around 7.4 ppm are signals corresponding to thearomatic protons of the benzene ring. The signals at about 5.9 ppm and5.3 ppm correspond to the protons of the double bond in the allyl amineportion of the compound.

FIG. II depicts the partial ¹H NMR spectrum, showing the region of δ5.0-8.0, of a latex formulation prepared according to Example #1 above.As can be seen in FIG. II, the double bond signals from he allyl amineportion of the compound, at 5.9 ppm and 5.3 ppm, are absent from thespectrum. Without being bound by any particular theory, the double bondhas been substantially completely consumed during the polymerizationreaction.

EXAMPLE 2 (COMPARATIVE EXAMPLE)

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA)co-polymer (in a weight ratio of about 48:49:3), in combination with thepropylamine salt of dodecylbenzenesulfonic acid (PDDBS), is prepared asfollows. About 330 g of deionized water and about 25 g of PDDBS (as a20% active aqueous solution) are placed in a reactor suitable foremulsion polymerization, equipped with agitation means, heating meansand cooling means. With agitation, the reactor is purged with nitrogen(99% pure), and heated to about 80-82° C. The temperature of the reactorcontents is adjusted to about 77-79° C., and about 75 g of the monomermixture (20% of a total of 374 g of the MMA/BA/MMA monomer mixture inthe ratio above) is added to the reactor. After 10 minutes, 15.5 g of asolution of ammonium persulfate (20% of the total solution of 1.9 g ofammonium persulfate dissolved in 75.6 g of water), is added to thereactor over a period of about 5 minutes with continued agitation,during which time there is an exotherm of about 3-5° C. After theexotherm is complete, about 299 g of the monomer mixture (the remaining80%) and 62 g of the ammonium persulfate solution (the remaining 80%)are simultaneously charged tot he reactor over a period of 2 hours withcontinued agitation, while keeping the reactor contents at a temperatureof about 78-82° C. The reactor temperature is then elevated to about82-84° C. with continued agitation, for about 15 minutes. After this 15minute period, the reactor is cooled to about 30° C. The resulting latexproduct is completely removed from the reactor and gravity filteredusing a first 20 mesh screen and then a second 250 mesh screen. Thetotal latex coagulum (i.e. solids) from both mesh screens is collected,combined and weighed. Various physiochemical properties of the latex arereported in Table II.

EXAMPLE 3

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BAIMMA)co-polymer (in a weight ratio of about 46.1:50.8:3.1) in combinationwith the allylamine salt of nonyl phenol 9-EO phosphate acid ester(Cedephos CP-610) is prepared as follows. About 249 g of deionized waterand about 11.0 g of the allyl amine salt of Cedephos CP-610 (as a 20%active aqueous solution), are placed in a reactor suitable for emulsionpolymerization, equipped with agitation means, heating means and coolingmeans. With agitation, the reactor is purged with nitrogen (99% pure),and heated to about 75 77° C. The temperature of the reactor contents isadjusted to about 71-74° C., and about 74 g of the monomer mixture (20%of a total of 371 g of the MMA/BA/MM monomer mixture in the ratio above)is added to the reactor. After 10 minutes, 15 g of a solution ofammonium persulfate (20% of the total solution of 1.9 g of ammoniumpersulfate dissolved in 74.0 g of water) is added to the reactor over aperiod of about 10 minutes with continued agitation, during which timethere is an exotherm of about 5-8° C. After the exotherm is complete,about 299 g of the monomer mixture (the remaining 80% MMA/BA/MMA monomermixture), 60.7 g of the ammonium persulfate solution (the remaining80%), and 15.3 g of the allyl amine salt of Cedephos CP-610 (as a 20%active aqueous solution) are simultaneously charged to the reactor overa period of 2 hours with continued agitation, while keeping the reactorcontents at a temperature of about 78-81° C. The reactor temperature isthen elevated to about 82-84° C. with continued agitation, for about 15minutes. After this 15 minute period, the reactor is cooled to about 30°C. The resulting latex product is completely removed from the reactorand gravity filtered using a first 20 mesh screen and then a second 250mesh screen. The total latex coagulum (i.e. solids) from both meshscreens is collected, combined and weighed. Various physiochemicalproperties of the latex are reported in Table II.

EXAMPLE 4 (COMPARATIVE EXAMPLE

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA)co-polymer (in a weight ratio of about 46:51:3), in combination with thepropylamine salt of nonyl phenol 9-EO phosphate acid ester (CedephosCP-610) is prepared as follows. About 251 g of deionized water and about10.2 g of propylamine salt of Cedephos CP-610 (as a 20% active aqueoussolution), are placed in a reactor suitable for emulsion polymerization,equipped with agitation means, heating means and cooling means. Withagitation, the reactor is purged with nitrogen (99% pure), and heated toabout 75 77° C. The temperature of the reactor contents is adjusted toabout 71-74° C., and about 75 g of the monomer mixture (20% of a totalof 375 g of the MMA/BA/MMA monomer mixture in the ratio above) is addedto the reactor. After 10 minutes, 15 g of a solution of ammoniumpersulfate (20% of the total solution of 1.9 g of ammonium persulfatedissolved in 75.0 g of water) is added to the reactor over a period ofabout 10 minutes with continued agitation, during which time there is anexotherm of about 8-10° C. After the exotherm is complete, about 300 gof the monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture),61.5 g of the ammonium persulfate solution (the remaining 80%), and 15.3g of the propylamine salt of Cedephos CP-610 (as a 20% active aqueoussolution) are simultaneously charged to the reactor over a period of 2hours with continued agitation, while keeping the reactor contents at atemperature of about 78-80° C. The reactor temperature is then elevatedto about 82-84° C. with continued agitation, for about 15 minutes. Afterthis 15 minute period, the reactor is cooled to about 30° C. Theresulting latex product is completely removed from the reactor andgravity filtered using a first 20 mesh screen and then a second 250 meshscreen. The total latex coagulum (i.e. solids) from both mesh screens iscollected, combined and weighed. Various physiochemical properties ofthe latex are reported in Table II.

EXAMPLE 5

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA)co-polymer (in a weight ratio of about (48:49:3), in combination withthe allylamine salt of lauric acid (ALA) is prepared as follows. About205 g of deionized water and about 1.6 g of ALA (as a 20% active aqueoussolution), are placed in a reactor suitable for emulsion polymerization,equipped with agitation means, heating means and cooling means. Withagitation, the reactor is purged with nitrogen (99% pure), and heated toabout 70-73° C. The temperature of the reactor contents is adjusted toabout 71-73° C., and about 75 g of the monomer mixture (20% of a totalof 374 g of the MMA/BA/MMA monomer mixture in the ratio above) is addedto the reactor. After 10 minutes, 15 g of a solution of ammoniumpersulfate (20% of the total solution of 1.8 g of ammonium persulfatedissolved in 75.0 g of water) is added to the reactor over a period ofabout 10 minutes with continued agitation, during which time there is anexotherm of about 2-3° C. After the exotherm is complete, about 299 g ofthe monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture), 61.5g of the ammonium persulfate solution (the remaining 80%), and 29.2 g ofthe ALA (as a 20% active aqueous solution) are simultaneously charged tothe reactor over a period of 2 hours with continued agitation, whilekeeping the reactor contents at a temperature of about 78-81° C. Thereactor temperature is then elevated to about 83-85° C. with continuedagitation, for about 15 minutes. After this 15 minute period, thereactor is cooled to about 30° C. The resulting latex product iscompletely removed from the reactor and gravity filtered using a first20 mesh screen and then a second 250 mesh screen. The total latexcoagulum (i.e. solids) from both mesh screens is collected, combined andweighed. Various physiochemical properties of the latex are reported inTable II.

EXAMPLE 6 (COMPARATIVE EXAMPLE)

A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA)co-polymer (in a weight ratio of about (48:49:3), in combination withthe propylamine salt of lauric acid (PLA) is prepared as follows. About206 g of deionized water and about 1.6 g of PLA (as a 20% active aqueoussolution), are placed in a reactor suitable for emulsion polymerization,equipped with agitation means, heating means and cooling means. Withagitation, the reactor is purged with nitrogen (99% pure), and heated toabout 75-77° C. The temperature of the reactor contents is adjusted toabout 71-73° C., and about 7 g of the monomer mixture (2% of a total of373 g of the MMA/BA/MMA monomer mixture in the ratio above) is added tothe reactor. After 10 minutes, 15 g of a solution of ammonium persulfate(20% of the total solution of 1.8 g of ammonium persulfate dissolved in75.0 g of water) is added to the reactor over a period of about 10minutes with continued agitation, during which time there is an exothermof about 2-3° C. After the exotherm is complete, about 366 g of themonomer mixture (the remaining 98% MMA/BA/MMA monomer mixture), 61.5 gof the ammonium persulfate solution (the remaining 80%), and 28.4 g ofthe PLA (as a 20% active aqueous solution) are simultaneously charged tothe reactor over a period of 2 hours with continued agitation, whilekeeping the reactor contents at a temperature of about 79-82° C. Thereactor temperature is then elevated to about 83-85° C. with continuedagitation, for about 15 minutes. After this 15 minute period, thereactor is cooled to about 30° C. The resulting latex product iscompletely removed from the reactor and gravity filtered using a first20 mesh screen and then a second 250 mesh screen. The total latexcoagulum (i.e. solids) from both mesh screens is collected, combined andweighed. Various physiochemical properties of the latex are reported inTable II.

TABLE II Latexes of Methylmethacrylate/Butylacrylate/Methacrylic AcidMechanical Particle Contact Method Coagulum Viscosity Stability SizeAngle of Surfactant (%) (CPS) (min) (microns) (deg.) pH Solids (%)Initiation Polymerizable <0.2  11  8 120.5 125 2.43 46.9 ThermalSurfactant ADDBS (Ex. 1) Non-Polymerizable <0.03 220   5 122.5  98 2.2344   Thermal Surfactant PDDBS (Compartive Ex. 2) Polymerizable <0.67 90ND 135   126 3.25 46.6 Thermal Surfactant Allylamine- Cedephos (Ex. 3)Non-Polymerizable <0.52 115  ND 149   104 2.92 47.7 Thermal SurfactantPDDBS (Comparative Ex. 4) Polymerizable <0.67 50 >15 1191   ND 5.7  49.7Thermal Surfactant ALA (Ex. 5) Non-Polymerizable <0.52 50 >15 1197.7  ND6.1  48.8 Thermal Surfactant PLA (Comparative Ex. 6)

EXAMPLE 7

A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio ofabout 78.9:21.1), in combination with the allylamine salt ofdodecylbenzenesulfonic acid (ADDBS) and propylamine salt ofdodecylbenzenesulfonic (PDDBS) is prepared as follows. About 245 g ofdeionized water and about 1.5 g of ADDBS (as a 20% active aqueoussolution), 1.5 g of PDDBS (as a 23% active aqueous solution), and 1.0 gof sodium sulfate are placed in a reactor suitable for emulsionpolymerization, equipped with agitation means, heating means and coolingmeans. With agitation, the reactor is purged with nitrogen (99% pure),and heated to about 65-68° C. The temperature of the reactor contents isadjusted to about 63-65° C., and about 73.7 g of the monomer mixture(20% of a total of 369 g of the VA/BA monomer mixture in the ratioabove) is added to the reactor. After 10 minutes, 15 g of a solution ofammonium persulfate (20% of the total solution of 1.8 g of ammoniumpersulfate dissolved in 75.0 g of water) is added to the reactor over aperiod of about 5 minutes with continued agitation. The temperature ofthe reactor is increased to about 82-84° C. Evidence of polymerizationis observed by the appearance of blue tint in the reaction contents anda slight exotherm of 1-2° C. The temperature of the reaction contents isadjusted to about 76-78° C. and about 294 g of the BA/VA monomer mixture(the remaining 80%), 61.5 g of the ammonium persulfate solution (theremaining 80%), 27.46 g ADDBS (as a 20% active aqueous solution), and8.59 g PDDBS (as a 23% active aqueous solution) are simultaneouslycharged to the reactor over a period of 4 hours with continuedagitation, while keeping the reactor contents at a temperature of about78-82° C. The reactor temperature is then elevated to about 82-84° C.with continued agitation, for about 15 minutes. After this 15 minuteperiod, the reactor is cooled to about 30° C. The resulting latexproduct is completely removed from the reactor and gravity filteredusing a first 20 mesh screen and then a second 250 mesh screen. Thetotal latex coagulum (i.e. solids) from both mesh screens is collected,combined and weighed. Various physiochemical properties of the latex arereported in Table III.

EXAMPLE 8 (COMPARATIVE EXAMPLE)

A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio ofabout 79.1:20.9), in combination with the propyl amine salt ofdodecylbenzenesulfonic acid (PDDBS) is prepared as follows. About 162 gof deionized water and about 5.4 g of PDDBS (as a 23% active aqueoussolution) are placed in a reactor suitable for emulsion polymerization,equipped with agitation means, heating means and cooling means. Withagitation, the reactor is purged with nitrogen (99% pure), and heated toabout 65-68° C. The temperature of the reactor contents is adjusted toabout 62° C., and about 5.0 g of the monomer mixture (2% of a total of245 g of the VA/BA monomer mixture in the ratio above) is added to thereactor. After 10 minutes, 10.1 g of a solution of ammonium persulfate(20% of the total solution of 1.8 g of ammonium persulfate dissolved in75.0 g of water) is added to the reactor over a period of about 15minutes with continued agitation. The temperature of the reactor isincreased to about 82-84° C. Evidence of polymerization is observed bythe appearance of blue tint in the reaction contents and a slightexotherm of 2-4° C. The temperature of the reaction contents is adjustedto about 76-78° C. and about 240 g of the BA/VA monomer mixture (theremaining 80%), 40.7 g of the ammonium persulfate solution (theremaining 80%), 16.8 g PDDBS (as a 23% active aqueous solution) aresimultaneously charged to the reactor over a period of 4 hours withcontinued agitation, while keeping the reactor contents at a temperatureof about 78-80° C. The reactor temperature is then elevated to about82-84° C. with continued agitation, for about 15 minutes. After this 15minute period, the reactor is cooled to about 30° C. The resulting latexproduct is completely removed from the reactor and gravity filteredusing a first 20 mesh screen and then a second 250 mesh screen. Thetotal latex coagulum (i.e. solids) from both mesh screens is collected,combined and weighed. Various physiochemical properties of the latex arereported in Table III.

EXAMPLE 9

A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio ofabout 78.9:21.1), in combination with the allylamine salt ofdodecylbenzenesulfonic acid (ADDBS) and the ammonium salt of laurylether sulphate with 30 EO groups (ALSE) is prepared as follows. About245 g of deionized water and about 1.5 g of ADDBS (as a 19% activeaqueous solution) and 1.0 g of sodium sulfate are placed in a reactorsuitable for emulsion polymerization, equipped with agitation means,heating means and cooling means. With agitation, the reactor is purgedwith nitrogen (99% pure), and heated to about 65-68° C. The temperatureof the reactor contents is adjusted to about 60-63° C., and about 73.7 gof the monomer mixture (20% of a total of 369 g of the VA/BA monomermixture in the ratio above) is added to the reactor. After 10 minutes,15 g of a solution of ammonium persulfate (20% of the total solution of1.8 g of ammonium persulfate dissolved in 75.0 g of water) is added tothe reactor over a period of about 5 minutes with continued agitation.The temperature of the reactor is increased to about 82-84° C. Evidenceof polymerization is observed by the appearance of blue tint in thereaction contents and a slight exotherm of 1-2° C. The temperature ofthe reaction contents is adjusted to about 78-81° C. and about 294 g ofthe BA/VA monomer mixture (the remaining 80%), 61.4 g of the ammoniumpersulfate solution (the remaining 80%), 27.8 g ADDBS (as a 20% activeaqueous solution), and 6.3 g ALSE (as a 30% active aqueous solution) aresimultaneously charged to the reactor over a period of 4 hours withcontinued agitation, while keeping the reactor contents at a temperatureof about 78-82° C. The reactor temperature is then elevated to about82-84° C. with continued agitation, for about 15 minutes. After this 15minute period, the reactor is cooled to about 30° C. The resulting latexproduct is completely removed from the reactor and gravity filteredusing a first 20 mesh screen and then a second 250 mesh screen. Thetotal latex coagulum (i.e. solids) from both mesh screens is collected,combined and weighed. Various physiochemical properties of the latex arereported in Table III.

EXAMPLE 10

A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio ofabout 78.9:21.1), in combination with the allylamine salt ofdodecylbenzenesulfonic acid (ADDBS) and propylamine salt ofdodecylbenzenesulfonic (PDDBS) is prepared, using redox couple asinitiators, as follows. About 251 g of deionized water and about 1.5 gof ADDBS (as a 19% active aqueous solution), 0.9 g of PDDBS (as a 23%active aqueous solution), and 0.3 g of sodium hydrogen carbonate areplaced in a reactor suitable for emulsion polymerization, equipped withagitation means, heating means and cooling means. With agitation, thereactor is purged with nitrogen (99% pure), and heated to about 65-68°C. The temperature of the reactor contents is adjusted to about 63-65°C., and about 10.3 g of the monomer mixture (2% of a total of 513 g ofthe VA/BA monomer mixture in the ratio above) is added to the reactor.After 15 minutes, 13.7 g of a solution of ammonium persulfate (20% ofthe total solution of 2.0 g of ammonium persulfate dissolved in 66.5 gof water) and 13.7 g of a solution of sodium metabisulfite (20% of thetotal solution of 0.83 g of sodium metabisulfite dissolved in 67.8 g ofwater) is added to the reactor over a period of about 5 minutes withcontinued agitation. Evidence of polymerization is observed by theappearance of blue tint in the reaction contents and a slight exothermof 1-2° C. The temperature of the reaction contents is adjusted to about68-72° C., and 54.9 g of the sodium metabisulphite solution (theremaining 80%), 54.8 g of the ammonium persulfate solution (theremaining 80%), 503 g of the BAIVA monomer mixture (the remaining 98%),29.3 g of ADDBS (as a 19% active aqueous solution), and 10.3 g of PDDBS(as a 23% active aqueous solution) are simultaneously added over aperiod of three hours with continued agitation, while keeping thereactor contents at a temperature of about 68-72° C. The reactortemperature is then elevated to about 75-78° C. with continuedagitation, for about 15 minutes. After this 15 minute period, thereactor is cooled to about 30° C. The resulting latex product iscompletely removed from the reactor and gravity filtered using a first20 mesh screen and then a second 250 mesh screen. The total latexcoagulum (i.e. solids) from both mesh screens is collected, combined andweighed. Various physiochemical properties of the latex are reported inTable III.

TABLE III Latexes of Vinylacetate/Butylacrylate Mechanical ParticleContact Method Coagulum Viscosity Stability Size Angle of Surfactant (%)(CPS) (min) (microns) (deg.) pH Solids (%) Initiation Polymerizable/Non-<0.09 220 >13 266/767  86 2.23 45.1 Thermal Polymerizable SurfactantsADDBS & PDDBS (Ex. 7) Non-Polymerizable <0.05  50  6   98.3 104 2.4841.2 Thermal Surfactant PDDBS (Compartive Ex. 8) Polymerizable/Non-<0.03  50 ND 1599  ND 2.63 45.3 Thermal Polymerizable Surtactants ADDBS& ALSE (Ex. 9) Polymerizable/Non- <0.06 220 ND 410 ND 5.23 46.6 RedoxPolymerizable Surfactants ADDBS & PDDBS (Ex. 10)

The hydrophobicity of a latex prepared using a typical non-polymerizablesurfactant was compared to that of a latex prepared using arepresentative polymerizable surfactant of the present invention. It hasbeen discovered that the latex prepared in Example 1 (using ADDBS)possess remarkable hydrophobicity, as compared to the latex preparedaccording to Example 1 (using the ammonium salt of dodecylbenzenesulfonic acid, AmDDBS). [Need to insert ASTM method and descriptionhere.] The change in contact angle as a function of time for a waterdroplet at each of the latex film surfaces was measured; the results areshown below.

Time (Seconds) Latex Surfactant 5 20 40 60 AmDDBS (Contact Angle)  98° 74°  51°  27° (non-polymerizable) ADDBS (polymerizable) (Contact Angle)125° 125° 125° 125°

Without being bound by any particular theory, a rapidly increasingcontact angle as observed from a latex film indicates that the waterdroplet is penetrating the film due to surfactant related imperfectionsof the film. A constant water droplet contact angle, as in the case ofthe ADDBS derived latex, indicates the desirable result whereby water isunable to penetrate the hydrophobic film.

In a test similar to the contact angle measurements, the hydrophobicityof a latex prepared using a typical non-polymerizable surfactant wascompared to that of a latex prepared using a representativepolymerizable surfactant of the present invention, whereby the differentlatex films were coated and heat cured onto porous filter paper andtreated with water. As observed in the results shown below, waterundesirably, readily penetrated through the film and absorbed into thepaper in a few seconds for the latex derived from the AmDDBS surfactant.However, the latex film derived from the ADDBS surfactant, did not allowthe water to penetrate or absorb; the water droplet maintained itsoriginal shape on the latex film, prior to being influenced byevaporation effects (at least thirty minutes).

Time (Seconds) Latex Surfactant 5 20 40 60 AmDDBS (penetration/ slighttotal total total (non-polymerizable) absorption) ADDBS (polymerizable)(penetration/ none none none none absorption)

The adhesion properties of a latex prepared using a typicalnon-polymerizable surfactant were compared to that of a latex preparedusing a representative polymerizable surfactant of the presentinvention. It has been discovered that the latex prepared in Example 1(using ADDBS) possess a vastly superior adhesion profile, as compared tothe latex prepared according to Example 1 (using the ammonium salt ofdodecylbenzene sulfonic acid, AmDDBS). Adhesion data were collect foreach latex acrylic lattice using ASTM method D897. This test method is astandard test for adhesion called “block pull”; results from the testare indicated in pounds per square inch (p.s.i.), wherein the higher thep.s.i. obtained, the better the adhesion properties of the latex.Adhesive failure is defined as the point at which the latex, uponapplication of a pulling force, no longer adheres to the surface of thesubstrate. Cohesive failure is defined as the point at which the latexitself fails, i.e. where the latex splits into two or more portions, butremains bound to the substrate. The adhesion tests were conducted usingan Instron Model 1123, with a 5000 pound load cell, a sample size of 0.5g of latex, a surface area of 4 in², whereby the treated sample blockswere allowed to dry at room temperature (i.e. 25° C.) for three daysunder 0.25 p.s.i. external pressure. Aluminum and steel blocks wereprepared by sanding with extra fine 220 grit paper until smooth to thetouch. A weighed amount of each latex (0.5 g) was placed on one surfaceof one block and another block place on top for three days. Failure wasdetermined by visual inspection, with the results indicated below.

Latex Surfactant Adhesive Failure (p.s.i.) AmDDBS (non-polymerizable) 65 ADDBS (polymerizable) 170

The latex film yellowing properties of a latex prepared using a typicalnon-polymerizable surfactant were compared to that of a latex preparedusing a representative polymerizable surfactant of the presentinvention. It has been discovered that the latex prepared in Example 1(using ADDBS) possess a greatly improved film yellowing profile, ascompared to the latex prepared according to Example 1 (using theammonium salt of dodecylbenzene sulfonic acid, AmDDBS). Latex filmyellowing was compared after aging the films six months at roomtemperature, at approximately standard atmospheric conditions. It ishighly desirable, as known by one skilled in the art, to produce a latexfilm which does not yellow upon application to a surface, with thepassage of time. After a period of 6 months, the ADDBS-derived latex wasplainly observed to be significantly lighter color than theAmDDBS-derived latex. Absorbence measurements were taken for each latexat 350 nm and 420 nm; the lower the absorbance at a given wave length,the lighter the latex (i.e. the less yellow the latex). Results of themeasurements for the two latexes are shown below.

Latex Absorbance Latex Surfactant 350 nm 420 nm AmDDBS(non-polymerizable) 16.9 5.3 ADDBS (polymerizable) 10.0 2.5

The scrubability properties of a latex prepared using a typicalnon-polymerizable surfactant were compared to that of a latex preparedusing a representative polymerizable surfactant of the presentinvention. It has been discovered that the latex prepared in Example 1(using ADDBS) possess improved scrubability characteristics, as comparedto the latex prepared according to Example 1 (using the ammonium salt ofdodecylbenzene sulfonic acid, AmDDBS). Scrubability of the latexes wasevaluated using ASTM scrub test D2486. Seven Star Acrylic Flat HousePaint, 103A100 White, from Ace Hardware was utilized in the testing. TheADBBS- and AmDDBS-derived latexes were individually added to the paintin a ratio of 2:1 (latex:paint).

FTIR comparisons were conducting by casting latex films on glass,derived from both ADDBS and AmDDBS. The films were dried at roomtemperature for several days, removed from the glass and aged at roomtemperature, at approximately standard atmospheric conditions, for sixmonths. The films were individually placed on a ZnSe plates and the FTIRspectra recorded. Peak heights were measured on the absorbance peaklocated at 1035 cm⁻¹ (i.e. the S=O stretch peak) for each film. It hasbeen discovered that the latex prepared in Example 1 (using ADDBS)possess a much lower peak height absorbance in the FTIR spectrum, ascompared to the latex prepared according to Example 1 (using theammonium salt of dodecylbenzene sulfonic acid, AmDDBS). Without beingbound by any particular theory, a lower the peak height absorbanceindicates a desirable characteristic of the latex, whereby theindividual surfactant molecules are not present at the surface of thelatex film, i.e. they have not migrated to the surface of the film.

Latex Surfactant Latex FTIR Absorbance (× 10⁻⁴) AmDDBS(non-polymerizable) 73 ADDBS (polymerizable) 29

From the foregoing, it will be appreciated that although specificembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit or scope of the invention.

What is claimed:
 1. A polymer comprising: a) at least one monomer unit;and b) at least one surface active agent unit; wherein the monomer unitis derived from an ethylenically unsaturated monomer; and the surfaceactive agent unit is derived from a polymerizable surface active agenthaving the formula:

where R_(n) and R_(m) independently represent hydrogen or methyl; and X⁻represents an anion selected from fatty alkyl benzene sulfonates, fattyalkyl carboxylates, fatty alkyl ether sulfates, fatty sulfates, andfatty alkyl phenol ethoxylates of phosphoric acid, where each fattyalkyl portion has from about 4-18 carbon atoms, and the ethylenicallyunsaturated monomer and the polymerizable surface active agent haveco-polymerized to form the polymer.
 2. A polymer according to claim 1,wherein R_(n) and R_(m) are not both methyl.
 3. A polymer according toclaim 1, wherein the anion is a fatty alkyl benzene sulfonate having theformula:

wherein n1=4-18; and R′ is hydrogen or saturated or unsaturatedhydrocarbon group having from about 1-8 carbon atoms.
 4. A polymeraccording to claim 1, wherein the polymerizable, surface active agentand the monomer are combined in a ration of about 0.01:1 to about 3:1 ona weight basis.
 5. A polymer according to claim 1, wherein a portion ofthe polymerizable, surface active agent is partially consumed bypolymerization with itself, co-polymerization with the monomer and/orco-polymerization with a partially polymerized polymer particle.
 6. Apolymer according to claim 3, wherein n1 is about 10 and R′ is hydrogen.7. A polymer according to claim 4, wherein n1 is about 10 and R′ ishydrogen.
 8. A polymer according to claim 5, wherein n1 is about 10 andR′ is hydrogen.